MetE 433

MATERIALS FOR ORGANIC ELECTRONICS

Instructor: Dr. Yusuf Keleştemur

Office: Metallurgical and Materials Engineering Department, Room: E – 212
Email: [email protected]
Phone: + 90 312 210 – 5911

Course Assistant: Ulaş Yaprak

Office: Metallurgical and Materials Engineering Department, Room: D - 228
Email: [email protected]
Phone: + 90 312 210 – 7485

Spring 2024 Y. Kelestemur 1

Elementary Quantum Physics
Photons

In introductory physics courses, light is considered to be a electromagnetic wave.

The classical view of light as an electromagnetic wave

Spring 2024 Y. Kelestemur 2

Elementary Quantum Physics
Photons

In introductory physics courses, light is considered to be a electromagnetic wave.

Indeed, such phenomena as interference, diffraction, refraction, and reflection can all be
explained by the theory of waves.

Spring 2024 Y. Kelestemur 3

Elementary Quantum Physics
Photons

Understanding the wave nature of light is fundamental to understanding interference

and diffraction.

Schematic illustration of Young’s double-slit experiment

Spring 2024 Y. Kelestemur 4

Elementary Quantum Physics
Photons

Understanding the wave nature of light is fundamental to understanding interference

and diffraction.

Diffraction patterns obtained by passing X-rays through crystals can only be explained
by using ideas based on the interference of waves

Spring 2024 Y. Kelestemur 5

Elementary Quantum Physics
The Photoelectric Effect

Aside from exhibiting wave-like properties, light can behave like a stream of “particles”
of zero rest-mass.

The photoelectric effect

Spring 2024 Y. Kelestemur 6

Elementary Quantum Physics
The Photoelectric Effect

1) The saturation current is proportional to the light intensity.

2) For a given frequency of light, increasing the intensity of light I requires the same
voltage V0 to extinguish the current.

V is the negative anode voltage

v is the velocity and
KEm is the kinetic energy of the electron

Photoelectric current versus voltage when the cathode is illuminated with light of
identical wavelength but different intensities

Spring 2024 Y. Kelestemur 7

Elementary Quantum Physics
The Photoelectric Effect

3) The stopping voltage and therefore the maximum kinetic energy of the emitted
electron increases with the frequency of light, f.

V is the negative anode voltage

v is the velocity and
KEm is the kinetic energy of the electron

Photoelectric current versus voltage when the cathode is illuminated with light of
different wavelengths and intensities

Spring 2024 Y. Kelestemur 8

Elementary Quantum Physics
The Photoelectric Effect

The successful interpretation of the photoelectric effect was first given in 1905 by
Einstein, who proposed that

light consists of “energy packets,” each of which has the magnitude hf.

Spring 2024 Y. Kelestemur 9

Elementary Quantum Physics
The Photoelectric Effect

The experimental results can be summarized by a statement that relates the KEm of the
electron to the frequency of light and the electrode metal, as follows

where h is the slope of the straight line and

is independent of the type of metal,

whereas f0 depends on the electrode material

for the photocathode,

the constant h is called Planck’s constant,

and equal to 6.6 × 10−34 J s.

The effect of varying the frequency of light and the cathode material
in the photoelectric experiment

Spring 2024 Y. Kelestemur 10

Elementary Quantum Physics
The Photoelectric Effect

The successful interpretation of the photoelectric effect was first given in 1905 by
Einstein, who proposed that

light consists of “energy packets,” each of which has the magnitude hf.

We can call these energy quanta photons.

E is the energy of photon

h is the Planck’s constant ( 6.6 × 10−34 J s)
c is the speed of light (3 × 108 m s−1)
𝒇𝒇 is the frequency of ligth
𝝀𝝀 is the wavelength of light
Spring 2024 Y. Kelestemur 11
Elementary Quantum Physics
Example : Energy of a Blue Photon

What is the energy of a blue photon that has a wavelength of 450 nm?

Spring 2024 Y. Kelestemur 12

Elementary Quantum Physics
Example : The Photoelectric Experiment

In the photoelectric experiment, green light, with a wavelength of 532 nm,

is the longest-wavelength radiation that can cause the photoemission of
electrons from a clean sodium surface.

a. What is the work function of sodium, in electron–volts (eV)?

b. If UV (ultraviolet) radiation of wavelength 240 nm is incident to the

sodium surface, what will be the kinetic energy of the photoemitted electrons,
in eV?

c. Suppose that the UV light of wavelength 240 nm has an intensity of 25

mW cm−2. If the emitted electrons are collected by applying a positive bias to
the opposite electrode, what will be the photoelectric current density?

Spring 2024 Y. Kelestemur 13

Elementary Quantum Physics
Compton Scattering

When an X-ray strikes an electron, it is deflected, or “scattered.”

Since the electron now also has a momentum pe, then from the conservation of linear
momentum law, we are forced to accept that the X-ray also has a momentum.

the momentum of the photon is related to its

wavelength by;

p is the momentum of a photon

h is the Planck’s constant ( 6.6 × 10−34 J s)
𝝀𝝀 is the wavelength of light Scattering of an X-ray photon by
a “free” electron in a conductor

Spring 2024 Y. Kelestemur 14

Elementary Quantum Physics
Particle – Wave Duality of Light

The photoelectric experiment and the Compton effect

are just two convincing experiments in modern physics that force us to accept that light
can have particle-like properties.

Photon energy and momentum

Spring 2024 Y. Kelestemur 15

Elementary Quantum Physics
The Electron as a Wave

Can electrons exhibit wave-like properties?

To check perform the interference and diffraction experiments.

Young’s double-slit experiment with electrons involves an electron gun and two
slits in a cathode ray tube (CRT) (hence, in vacuum)

Spring 2024 Y. Kelestemur 16

Elementary Quantum Physics
The Electron as a Wave

Can electrons exhibit wave-like properties?

To check perform the interference and diffraction experiments.

When an electron beam in a vacuum tube is passed through an Al foil, a

diffraction pattern is produced as the X-rays interact with the planes of atoms
in the Al sample

Spring 2024 Y. Kelestemur 17

Elementary Quantum Physics
The Electron as a Wave

As a result of such studies and other similar experiments, it has been found
that an electron traveling with a momentum p behaves like a wave of
wavelength λ given by

It is an equation that exposes the wave–particle duality of nature. It was

first hypothesized by de Broglie (1924).

Spring 2024 Y. Kelestemur 18

Elementary Quantum Physics
Particle or Wave ?

What is the wavelength of 50 gram golf ball travelling at a velocity of 20 m s-1 ?

What is the wavelength of electron accelerated by 100 V ?

Spring 2024 Y. Kelestemur 19

Elementary Quantum Physics
Particle or Wave ?

Spring 2024 Y. Kelestemur 20

Elementary Quantum Physics
Time-independent Schrödinger Equation

There is a general equation that describes this wave-like behavior and, with the
appropriate potential energy and boundary conditions, will predict the results of
the experiments.

The equation is called the Schrödinger equation and it forms the

foundations of quantum theory.

The fundamental equation that describes the electron’s behaviour by

determining 𝜓𝜓(x) is called the time-independent Schrödinger equation.

m is the mass of the electron

V is the potetial energy
E is the energy of the electron

Spring 2024 Y. Kelestemur 21

Elementary Quantum Physics
Infinite Potential Well: A Confined Electron

Consider the behavior of the electron in a one-dimesional infinite potential well;

- It is confined to a certain region 0 < x < a, and

- Its PE is zero inside that region and infinite outside.

Spring 2024 Y. Kelestemur 22

Elementary Quantum Physics
Infinite Potential Well: A Confined Electron

After the solution, it is found that the energy of the electron, can only have
certain values; they are quantized by virtue of n being an integer.

Energy of electron is calculated by;

E energy of electron in the nth state

h is the Planck’s constant
m is the mass of electron
a is the width of potential well
n is the quantum number
Spring 2024 Y. Kelestemur 23
Elementary Quantum Physics
Example: Electron Confined Within Atomic Dimensions

Consider an electron in an infinite potential well of size 0.1 nm (typical size of

an atom). What is the ground energy of the electron? What is the energy
required to put the electron at the second energy level? How can this energy
be provided?

Spring 2024 Y. Kelestemur 24

Elementary Quantum Physics
Three Dimensional Representation of Atomic Orbitals

Spring 2024 Y. Kelestemur 25

Modern Theory of Solids
Hydrogen Molecule: Molecular Orbital Theory of Bonding

Consider what happens when two hydrogen atoms approach each other to
form the hydrogen molecule. This is the H–H (or H2) system.

We use a molecular orbital 𝜓𝜓, which depends on the interaction of individual

atomic wavefunctions.

Spring 2024 Y. Kelestemur 26

Modern Theory of Solids
Hydrogen Molecule: Molecular Orbital Theory of Bonding

In the H2 molecule, we cannot have two sets of identical atomic 𝜓𝜓1s orbitals, for
two reasons;

1) This would violate the Pauli exclusion

principle.

2) The atomic 𝜓𝜓1s wavefunctions

overlap producing two new
wavefunctions with different energies
and hence different quantum
numbers.

Spring 2024 Y. Kelestemur 27

Modern Theory of Solids
Hydrogen Molecule: Molecular Orbital Theory of Bonding

Schematic diagram showing the changes in the electron energy as two isolated
H atoms, far left and far right, come together to form a hydrogen molecule.

Spring 2024 Y. Kelestemur 28

Modern Theory of Solids
Hydrogen Molecule: Molecular Orbital Theory of Bonding

Consider what happens when two He atoms come together.

Two He atoms have four electrons. When He atoms come together, two of the
electrons enter the E𝜎𝜎 level and two the E𝜎𝜎* level, so the overall energy is
greater than two isolated He atoms.

Spring 2024 Y. Kelestemur 29

Modern Theory of Solids
Energy Band Formation

Now consider the formation of a solid. Take N Li (lithium) atoms from infinity
and bring them together to form the Li metal.

The formation of a 2s energy band from the 2s orbitals when N Li atoms

come together to form the Li solid.
Spring 2024 Y. Kelestemur 30
Modern Theory of Solids
Energy Band Formation

As Li atoms are brought together from infinity, the atomic orbitals overlap and
give rise to bands (Schematic only)

Outer orbitals overlap first. The 3s orbitals give rise to the 3s band, 2p orbitals
to the 2p band, and so on.

Spring 2024 Y. Kelestemur 31

Modern Theory of Solids
For Metals

In a metal, the various energy bands overlap to give a single energy band that
is only partially full of electrons.

Fermi energy is the maximum energy of the electrons in a metal at 0 K.

Spring 2024 Y. Kelestemur 32

Modern Theory of Solids
For Semiconductors

The Si atom has 14 electrons, which distribute themselves in the various atomic
energy levels as shown in Figure.

When two Si atoms approach, 3s and 3p level electrons strongly interact with
each other. Therefore, in studying the formation of bands in the Si solid, we will
only consider these electrons.

The electronic structure of Si and isolated Si atom

Spring 2024 Y. Kelestemur 33

Modern Theory of Solids
For Semiconductors

Formation of energy bands in the Si crystal first involves hybridization (sp3) of

3s and 3p orbitals to four identical 𝜓𝜓hyb orbitals, which are at 109.5°

Spring 2024 Y. Kelestemur 34

Modern Theory of Solids
For Semiconductors

A simplified energy band diagram of a semiconductor.

CB is the conduction band and VB is the valence band.

At 0 K, the VB is full of electrons and the CB is empty.

Spring 2024 Y. Kelestemur 35

Modern Theory of Solids
For Semiconductors

(a) Energy band diagram of intrinsic semiconductor. (b) Density of states

(number of states per unit energy per unit volume). (c) Fermi–Dirac probability
function (probability of occupancy of a state). (d) The product of g(E) and f(E)
is the energy density of electrons in the CB (number of electrons per unit
energy per unit volume).
Spring 2024 Y. Kelestemur 36
Organic Materials
Atomic Orbitals of Carbon Materials

In a neutral and stable isotope of carbon atom 12C, there are six protons and
six electrons, and Valence Electrons

the electronic configuration of is simplified as 1s2 2s2 2p2

Shapes of some representative atomic electron orbitals

In chemistry, hybridization is the concept of mixing atomic orbitals to form

new hybrid orbitals suitable for the qualitative description of atomic bonding
properties.

Spring 2024 Y. Kelestemur 37

Organic Materials
Atomic Orbitals of Carbon Materials

sp3 hybridization

Spring 2024 Y. Kelestemur 38

Organic Materials
Atomic Orbitals of Carbon Materials

sp2 hybridization

Spring 2024 Y. Kelestemur 39

Organic Materials
Atomic Orbitals of Carbon Materials

sp hybridization

Spring 2024 Y. Kelestemur 40

Organic Materials
Molecular Orbitals of Carbon Materials

When the two s atomic orbitals overlap in phase, a σ bonding MO is formed.

Scheme of a pair of σ-type MOs formed from the overlap of two s atomic orbitals
Spring 2024 Y. Kelestemur 41
Organic Materials
Molecular Orbitals of Carbon Materials

When the two p atomic orbitals overlap in phase, a 𝝅𝝅 bonding MO is formed.

Scheme of a pair of σ-type MOs formed from the overlap of two s atomic orbitals
Spring 2024 Y. Kelestemur 42
Organic Materials
Molecular Orbitals of Carbon Materials

When the two spn atomic orbitals overlap in phase, a 𝝅𝝅 bonding MO is formed.

Scheme of a pair of σ-type MOs formed from the overlap of two spn atomic orbitals
Spring 2024 Y. Kelestemur 43
Organic Materials
Molecular Orbitals of Carbon Materials

sp2 hybridization

Schematic representation of C–C double 𝜋𝜋 bonds, represented in

(a) the chemical structure of ethene (ethylene),

(b) the scheme of double bond formation by overlapping/coupling of two vertically

aligned pz orbitals at two adjacent carbon sites,

(c) the schematic shape of a 𝜋𝜋 bonding orbital

Spring 2024 Y. Kelestemur 44

Organic Materials
Molecular Orbitals of Carbon Materials

1,3-Butadiene
4 Carbons with sp2 Hybridized Orbitals 4 Frontier pz Orbitals for 𝝅𝝅-Bonding

𝜋𝜋2 is the Highest Occupied Molecular

Orbital (HOMO) Energy Level

𝜋𝜋3* is the Lowest Unoccupied Molecular

Orbital (LUMO) Energy Level

Spring 2024 Y. Kelestemur 45

Organic Materials
Molecular Orbitals of Carbon Materials

Example:

Spring 2024 Y. Kelestemur 46

Organic Materials
Molecular Orbitals of Carbon Materials

Example:

Spring 2024 Y. Kelestemur 47

Organic Materials
Molecular Orbitals of Carbon Materials

Schematic representation of the evolution of excitation energy gap (Eg) versus

the number of repeat units in a conjugated organic system illustrating the
“particle-in-a-box” principle.

Spring 2024 Y. Kelestemur 48

Organic Materials
Molecular Orbitals of Carbon Materials

At what point does the molecular picture give way to the solid?

Spring 2024 Y. Kelestemur 49

Organic Materials
Molecular Orbitals of Carbon Materials

Isolated molecules readily can demonstrate discrete energy levels, as depicted for
the isolated case of 1,3-butadiene on the previous slide.

However, this does not translate well to discrete energy levels because we will now
have > 1023 molecules present for macroscopic solid-state organic electronic devices.

Solid State LUMO

Therefore, bands of energy form to

create the HOMO and LUMO
Energy Band Gap Energy (Eg)
energy levels observed in the solid
state.

Solid State HOMO

Spring 2024 Y. Kelestemur 50

Organic Materials
Molecular Orbitals of Carbon Materials

In general, the following properties of molecules;

- the more ordered and less distorted packing of molecules,

- the more well-defined solid-state structural periodicity,

- the better coupling between electronic orbitals of adjacent carbon sites

- the weaker lattice thermal vibrations or less electron–lattice (electron–phonon)

vibronic coupling (i.e., at lower temperatures),

the larger the bandwidth and the smaller the bandgap

Spring 2024 Y. Kelestemur 51

Organic Materials
Analogies between Inorganic and Organic Semiconductors

The mechanism of bonding (and transport) in inorganic semiconductors

(e.g., Si, GaAs) is different from organic semiconductors in a distinct manner.

However, analogies can be (and often are) drawn between the inorganic
semiconductor nomenclature and the organic semiconductor nomenclature. As
such, we need to be aware of these similarities, but it should be noted that
there is not a 1-to-1 similarity.

1) The HOMO energy level is like the valence band in the inorganic
semiconductor literature.

2) The LUMO energy level is like the conduction band in the inorganic
semiconductor literature.

3) The bandgap energy difference between the HOMO and LUMO energy
levels is similar to the bandgap energy for intrinsic inorganic semiconductor
literature.

Spring 2024 Y. Kelestemur 52

Organic Materials
Electronic Transitions in Organic Molecules
Jablonski’s diagram depicting major transitions of a material in energy regime

Spring 2024 Y. Kelestemur 53