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 –

Spring 2024 Y. Kelestemur 1

Organic Semiconductors
First: Establishing a vocabulary

without a common language, there can be no common understanding

- Illustration of molecular structure

- Basic molecular units and structures

- Standard terminologies

Spring 2024 Y. Kelestemur 2

Organic Semiconductors
First: Establishing a vocabulary

Benzene : C6H6

Phenyl: The phenyl group or phenyl ring is a cyclic group of atoms with the formula
C6H5. Phenyl groups are closely related to benzene.

Aryl: A functional group derived from an aromatic ring, usually an aromatic

hydrocarbon, such as phenyl and naphthy.

Spring 2024 Y. Kelestemur 3

Organic Semiconductors
First: Establishing a vocabulary

Alkanes are the simplest organic molecules, consisting of only carbon and hydrogen
and with only single bonds between carbon atoms.

Alkanes are the basis for naming the majority of organic compounds (their
nomenclature). Alkanes have the general formula CnH2n+2.

Spring 2024 Y. Kelestemur 4

Organic Semiconductors
First: Establishing a vocabulary

Polyacenes: The acenes or polyacenes are a class of organic compounds, and

polycyclic aromatic hydrocarbons made up of linearly fused benzene rings.

n = 1 corresponds to benzene, 2 = naphthalene, 3 = anthracene, 4 = tetracene, 5 =

pentacene, 6 = hexithene and so on…

Spring 2024 Y. Kelestemur 5

Organic Semiconductors
First: Establishing a vocabulary

Aromaticity: materials consisting of closed carbon rings where the C bonds are in
resonance.

- Double-single bond structure of the molecule allows the bond arrangement to

alternate between C atom pairs in the ring.

- To be aromatic the molecule must be planar and have an odd number of 𝝅𝝅

electron pairs.

Polycyclic Aromatic Hydrocarbon (PAH): Organic compounds containing only

carbon and hydrogen—that are composed of multiple aromatic rings (organic rings in
which the electrons are delocalized)

Spring 2024 Y. Kelestemur 6

Organic Semiconductors
First: Establishing a vocabulary

Heterocyclic compound or ring structure is a cyclic compound that has atoms of at

least two different elements as members of its ring(s).

Common heterocycles found in organic electronic molecules

Spring 2024 Y. Kelestemur 7

Organic Semiconductors
Types of Organic Semiconductors

Organic semiconductors are based on the fact that the sp2 hybridization of carbon in a
double bond leaves a pz orbital available for 𝜋𝜋 bonding.

The electrons in the 𝜋𝜋 bond can be delocalized via conjugation with neighbouring
𝜋𝜋 bonds, thus giving rise to charge carrier mobility.

1 – Small organic molecules

2 – Conjugated Polymers

Spring 2024 Y. Kelestemur 8

Organic Semiconductors
Small Organic Molecules

We can describe the small organic molecules as organics with a well-defined

molecular weight.

It is possible obtain both molecular crystals and amorphous molecular films by

using small organic molecules.

Chemical structures of 𝜋𝜋 - conjugated molecules that tend to form molecular crystals

Spring 2024 Y. Kelestemur 9

Organic Semiconductors
Small Organic Molecules

Molecular Crystals: Typical crystal-forming molecules are flat, large, aromatic

molecules such as the polyacenes, perylene, and similar compounds.

Comparison between inorganic and organic crystals

In commonly used inorganic crystals such as Si, NaCl; the atoms are kept together by
primary bonds including covalent and/or ionic bonding.

On the other hand, the small organic molecules being an electrically neutral molecules
are kept together by comparatively weak van-der-Waals interactions.
Spring 2024 Y. Kelestemur 10
Organic Semiconductors
Small Organic Molecules

Molecular Crystals

Crystal structure = lattice + basis

For a typical solid inorganic crystals basis is formed by atoms.

On the other hand, for organic molecular crystals basis is formed by organic
molecules.

The unit cell for the naphthalene, anthracene, tetracene, and pentacene

Spring 2024 Y. Kelestemur 11

Organic Semiconductors
Small Organic Molecules

Molecular Crystals

Views of the crystal structures of

(a) α-PTCDA is a closely packed, monoclinic lamellar structure and
(b) NTCDA forms a more open herringbone monoclinic lattice
Spring 2024 Y. Kelestemur 12
Organic Semiconductors
Small Organic Molecules

Molecular Layer Structures

Epitaxial growth, or epitaxy, is achieved when the lattice structure of the film
matches that of the substrate, that is, when the lattice of the adlayer atoms or
molecules is identical to that of the underlying substrate.

Strain is defined as the degree of lattice

Mismatch between two contacting layers.

The lattice mismatch for a cubic structure is

given by;

∆𝑎𝑎 = 𝑎𝑎𝑠𝑠 − 𝑎𝑎𝐸𝐸

Spring 2024 Y. Kelestemur 13

Organic Semiconductors
Small Organic Molecules

Molecular Layer Structures

Three possible layer schemes of a misfit lattice on a substrate.

(a) commensurate, (b) coincident, and (c) incommensurate.

The square substrate lattice is shown by open circles and the overlayer structure is
shown by filled circles. Coincidence in (a) and (b) is highlighted by red points.

Spring 2024 Y. Kelestemur 14

Organic Semiconductors
Small Organic Molecules

Growth Modes of Epitaxial Layers

Growth modes of epitaxial layers are described in three different ways;

(a) Layer-by-layer(Frank–van der Merwe),

(b) layer-plus-island (Stranski–Krastanov), and
(c) island (Volmer–Weber) growth.

The substrate lattice is in black, and the epitaxy is in red.

Spring 2024 Y. Kelestemur 15

Organic Semiconductors
Small Organic Molecules

Growth Modes of Epitaxial Layers

Examples from small organic molecules

PTCDA on graphite pentacene on polyimide ferrocene on Ag (110)

Spring 2024 Y. Kelestemur 16

Organic Semiconductors
Small Organic Molecules

Growth Modes of Epitaxial Layers

A particular attribute of weak van der Waals forces is the ability to achieve long
range order in layers grown onto substrates where there is substantial strain between
the contacting lattices.

Spring 2024 Y. Kelestemur 17

Organic Semiconductors
Small Organic Molecules

Amorphous Molecular Films

With this class of materials we associate molecules that form amorphous films, that is,
glasses, which are suitable for organic semiconductor applications.

Spring 2024 Y. Kelestemur 18

Organic Semiconductors
Conjugated Polymers

The name polymer is composed of the Greek words 𝜋𝜋𝜋𝜋𝜋𝜋𝜋𝜋 and 𝜇𝜇𝜇𝜇𝜇𝜇𝜇𝜇𝜇𝜇, meaning

“many” and “part”

In the context of organic semiconductors, “many” usually means at least 100 repeat
units.

The backbone of a semiconducting polymer is formed by a chain of carbon atoms with

alternating single and double bonds. Aromatic and heteroaromatic rings may also form
part of this structure.

Spring 2024 Y. Kelestemur 19

Organic Semiconductors
Conjugated Polymers

Average Molecular Weights of Polymers

The synthesized polymers do not all have exactly the same number of repeat units,
instead, there will be a distribution of polymer sizes. It can then be characterized by the
average weight of the polymer and the width of the associated weight distribution.

1) The number-average molecular weight 𝑴𝑴𝒏𝒏

2) The weight-average molecular weight 𝑴𝑴𝑾𝑾

Spring 2024 Y. Kelestemur 20

Organic Semiconductors
Conjugated Polymers

Average Molecular Weights of Polymers

Example

Consider a sample that contains 9 mole of polymers with a molecular weight of 10 000
Da and 5 mole of polymers with a molecular weight of 50 000 Da. (The abbreviation Da
stands for dalton, a synonym for atomic mass unit amu)

Spring 2024 Y. Kelestemur 21

Organic Semiconductors
Conjugated Polymers

Average Molecular Weights of Polymers

The spread of the distribution can be indicated by the polydispersity index PDI,
defined as the ratio between the weight-average and the number-average.

For the previous example;

𝑃𝑃𝑃𝑃𝑃𝑃 = 39/24 = 1.62

The distribution of molecular mass for a sample of the polymer MEH-PPV

Spring 2024 Y. Kelestemur 22

Organic Semiconductors
Conjugated Polymers

Polymer Structures and Their Names

By definition, a polymer is made up by a sequence of repeating units. There are,

however, many ways how such as sequence can be arranged.

If all repeat units are identical, they form a homopolymer.

While copolymers are formed when different repeat units are joint such as A and B.

For example, for two units A and B, the sequence of

…ABABABABABABABAB… defines an alternating copolymer,

…ABBAABABBBAABAABBA… is a statistical copolymer, and

…AAAAAAAABBBBBBBBBB… is a diblock copolymer.

Spring 2024 Y. Kelestemur 23

Organic Semiconductors
Conjugated Polymers

Polymer Structures and Their Names

In the majority of currently used semiconducting polymers, the electronically relevant

part of the repeat unit forms part of the polymer backbone. They are referred to as
main chain polymers.

There are, however, also a number of side chain polymers, where the backbone is
formed by the electronically inert molecular sections.

Spring 2024 Y. Kelestemur 24

Organic Semiconductors
Conjugated Polymers

Polymer Structures and Their Names

For some polymer chains, the relative position of the side chain in a sequence can be
relevant.

Thiophene rings may be connected (a) either head-to-tail, tail-to-tail, or head-to-head.

The numbering of the atoms is shown in gray. (b) If all connections are head-to-tail, the
resulting structure is regioregular, otherwise it is regiorandom.
Spring 2024 Y. Kelestemur 25
Organic Semiconductors
Conjugated Polymers

Importance of Side Chain

The large majority of today’s semiconducting polymers contain side chains that

- render the solubility of polymers in common organic solvents

- keep polymer chains at a certain distance from each other control the relative
orientation of polymer chains to each other.

- degree of electronic interaction

Poly(p-phenylene vinylene) (PPV) without sidechains, with linear alkyl sidechains, with
linear alkoxy sidechains, and with branched, asymmetric alkoxy sidechains
Spring 2024 Y. Kelestemur 26
Organic Semiconductors
Conjugated Polymers

Crystallinity of Polymers

• Ordered atomic arrangements

involving molecular chains
• Crystal structures in terms of
unit cells
• Example shown
• polyethylene unit cell

Spring 2024 Y. Kelestemur 27

Organic Semiconductors
Conjugated Polymers

Crystallinity of Polymers

Polymers rarely 100% crystalline

Difficult for all regions of all chains to
become aligned
crystalline
region
• Degree of crystallinity
expressed as % crystallinity.

amorphous
region

Spring 2024 Y. Kelestemur 28

Organic Semiconductors
Characterization of Conjugated Polymers

Here, I would like to cover some widely used characterization tools used for;

• Determination of the molecular weight of polymer semiconductors

• Evaluation of the chemical composition and regioregularity of polymer

semiconductors

• Quantifying the thermal transitions of polymer semiconductors

• Evaluating Crystal Structure and Orientation in Thin Films

• Quantification of the Optical Properties of Conjugated Polymers

Spring 2024 Y. Kelestemur 29

Organic Semiconductors
Characterization of Conjugated Polymers

Size Exclusion Chromatography (SEC)

SEC sends a dilute solution of a polymer semiconductor sample through a packed
column.

Spring 2024 Y. Kelestemur 30

Organic Semiconductors
Characterization of Conjugated Polymers

Size Exclusion Chromatography (SEC)

In this approach, well-known polymers are used to create a calibration curve.

Spring 2024 Y. Kelestemur 31

Organic Semiconductors
Characterization of Conjugated Polymers

Matrix Assisted Laser Desorption Ionization Time-of-Flight (MALDI-TOF)

Spring 2024 Y. Kelestemur 32

Organic Semiconductors
Characterization of Conjugated Polymers

Matrix Assisted Laser Desorption Ionization Time-of-Flight (MALDI-TOF)

MALDI-TOF measures discrete sizes of polymer chains as opposed to providing a

continuum curve like SEC.

Spring 2024 Y. Kelestemur 33

Organic Semiconductors
Characterization of Conjugated Polymers

Comparison of SEC and MALDI

Spring 2024 Y. Kelestemur 34

Organic Semiconductors
Characterization of Conjugated Polymers
1H NMR Spectroscopy

Proton Nuclear Magnetic Resonance (1H NMR) Spectroscopy determines the composition
and provides a molecular fingerprint of the polymer semiconductors. Based on the local
chemical environment, the hydrogen atoms associated with the molecule will have
different (well-characterized) chemical shifts.

Spring 2024 Y. Kelestemur 35

Organic Semiconductors
Characterization of Conjugated Polymers
1H NMR Spectroscopy

We can determine Mn of polymers.

Spring 2024 Y. Kelestemur 36

Organic Semiconductors
Characterization of Conjugated Polymers

Differential Scanning Calorimetry (DSC)

Spring 2024 Y. Kelestemur 37

Organic Semiconductors
Characterization of Conjugated Polymers

Typical DSC Procedure for Polymeric Materials

Spring 2024 Y. Kelestemur 38

Organic Semiconductors
Characterization of Conjugated Polymers

Crystallinity in Polymeric Materials

Spring 2024 Y. Kelestemur 39

Organic Semiconductors
Characterization of Conjugated Polymers

Classic Semiconducting Polymer Crystal Structure: P3HT

Spring 2024 Y. Kelestemur 40

Organic Semiconductors
Characterization of Conjugated Polymers

Evaluating Crystal Structures Using X-Ray Scattering

Spring 2024 Y. Kelestemur 41

Organic Semiconductors
Characterization of Conjugated Polymers

Evaluating Crystal Structure and Orientation in Thin Films

Grazing-Incidence Wide Angle X-Ray Scattering (GI-WAXS)

Spring 2024 Y. Kelestemur 42

Organic Semiconductors
Characterization of Conjugated Polymers

Evaluating Crystal Structure and Orientation in Thin Films

Grazing-Incidence Wide Angle X-Ray Scattering (GI-WAXS)

Spring 2024 Y. Kelestemur 43

Organic Semiconductors
Characterization of Conjugated Polymers

Quantification of the Optical Properties of Conjugated Polymers

Ultraviolet-Visible (UV-Vis) Light Spectroscopy

Spring 2024 Y. Kelestemur 44

Organic Semiconductors
Characterization of Conjugated Polymers

Quantification of the Optical Properties of Conjugated Polymers

Large Difference in Absorption Between Solution and the Solid States

Spring 2024 Y. Kelestemur 45