Organic Electronic Devices

Week 1: Semiconductor Synthesis and Characterization

Lecture 1.1: An Introduction to Organic Electronic Materials

Bryan W. Boudouris
Chemical Engineering
Purdue University

1
 Lecture Overview and Learning Objectives

• Concepts to be Covered in this Lecture Segment

• Chemical Structures of Organic Semiconductors

• Nomenclature of Common Organic Semiconducting Materials
• Design Considerations for Small Molecule and Macromolecular Organic
Semiconducting Materials
• Molecular Weight Characterization of Polymer Semiconductors

• Learning Objectives
By the Conclusion of this Presentation, You Should be Able to:

1. Draw the chemical structure of a common organic semiconductor given

the name and/or recite the name of an organic semiconductor given
the chemical structure of the material.
2. Predict the relative properties of two organic semiconductors given the
chemical structure of the two materials.
3. Calculate the number-average molecular weight, weight-average
molecular weight, and dispersity of a semiconducting polymer.
Understanding Device Operation Requires Knowledge of Materials

Organic Light-emitting Device (OLED) Displays

Thin and Lightweight Flexible Transparent

Sony Samsung Polytron

Organic Photovoltaic (OPV) Devices

Large Area Production Portable Applications Conformal Coverage

Konarka Konarka Konarka

 General Characteristics of Organic Semiconductors
• In this course, an organic semiconductor has the following properties.

1. The material is composed primarily of carbon, hydrogen, and oxygen.

Other atoms may be present in the material, but the majority (> 90%) of the
mass in these materials will be hydrocarbon-based.

2. In general, the organic semiconductors will contain a great deal of alternating

single and double bonds (i.e., they are π-conjugated materials).

3. Organic semiconductors are van der Waals solids that have covalent bonds
between the atoms of the materials.
Single Crystals Semicrystalline Nearly Amorphous

Podzorov Research Group, Tonazzini, I.; et al. Biophys. J. van Dijken, J. G.; Fleischauer,
http://www.physics.rutgers.edu/~ 2010, 98, 2804. M. D.; Brett, M. J. J. Mater.
podzorov/index.php Scale Bar = 1 µm Chem. 2011, 21, 1013.
Commonly-used Small Molecule Organic Semiconductors
Primarily Hole Transporting (p-type) Organic Semiconductors

Pentacene

Metal (e.g., Cu or Zn)

TIPS-Pentacene Rubrene Phthalocyanines (Pc)
Primarily Electron Transporting (n-type) Organic Semiconductors

Buckminsterfullerene PCBM PTCBI

(C60)
Further Reading: Mishra, A.; Bäuerle, P. Angew. Chem. Int. Ed. 2012, 51, 2020.
 Commonly-used Polymeric Organic Semiconductors
Primarily Hole Transporting (p-type) Polymer Semiconductors

P3AT

MEH-PPV

PBDTTT-C PDTP-DFBT PEDOT:PSS

Primarily Electron Transporting (n-type) Polymer Semiconductors

CN-MEH-PPV BBL
P(NDI2OD-T2) PT01
Further Reading: Boudouris, B. W. Curr. Opin. Chem. Eng. 2013, 2, 294.
 Design Considerations for Polymer Electronic Materials

• Increases in Polymer Backbone Conjugation and Thin Film

Crystallinity Tends to Improve the Charge Transport Ability

• Higher Molecular Weight Leads to Higher Degrees of Crystallinity

• Narrow Molecular Weight Distributions Lead to Higher Degrees of
Crystallinity
• Fused Rings Add to the Degree of Conjugation of the Polymer. This
Leads to More Charge Delocalization and, Generally, To a Better Ability
to Transport Charge

• Side Chains Are Used to Increase Solubility But Can Have Secondary
Effects with Respect to Thin Film Structure

• Branched Side Chains Help Increase the Solubility of the Organic

Electronic Materials Greatly
• Side Chains Can Impact the Thermal, Structural, and Optoelectronic
Properties of the Polymers by Changing the Solid State Packing
 Case Study: Poly(3-alkylthiophenes) (P3ATs)

Powder WAXS Patterns UV-Vis Absorption Spectra

μh ~ 10-4 cm2 V-1s-1

μh ~ 6 x 10-4 cm2 V-1s-1

μh ~10-3 cm2 V-1s-1

Polymers in ~1 μM chloroform solutions

Spun-coat from chloroform for a
Final film thickness of ~80 nm
Further Reading: Ho, V.; Boudouris, B. W.; Segalman, R.
A. Macromolecules 2010, 43, 7895.
Determination of the Number-average Molecular Weight (Mn)
Polymers Contain a Mixture of Macromolecular Sizes
6-mer 10-mer 16-mer

M0 = 100 g mol-1
Molar Mass of a Repeat Unit: M0
Molecular Weight of an i-mer with i number of repeat units: Mi = i× M0
ni
Mole Fraction of an i-mer: xi =
∑ ni
i
∑M n i i ∑ in i
Number-average Molecular Weight: M n = ∑ xi M i = i
= M0 i

i ∑n i
i ∑n
i
i

∑ in (1× 6) + (2 ×10) + (1×16)

= (100 g mol )×
i
−1 −1
Mn = M0 i
= 1,050 g mol
∑ni
i 1+ 2 +1
 Determination of the Weight-average Molecular Weight (Mw)
Polymers Contain a Mixture of Macromolecular Sizes
6-mer 10-mer 16-mer

M0 = 100 g mol-1
Molar Mass of a Repeat Unit: M0
Molecular Weight of an i-mer with i number of repeat units: Mi = i× M0
ini
Weight Fraction of an i-mer: wi =
∑ ini
i
∑ ini M i ∑ ni
i 2

Weight-average Molecular Weight: M w = ∑ wi M i = i

= M0 i

i ∑ ini
i ∑ ini
i

∑ in i
(1× 6 ) + (2 ×10 ) + (1×16 )
2 2 2
Mw =
M (
=
i
100 g mol ) × −1
=
1,171 g mol −1

∑n (1× 6) + (2 ×10) + (1×16)

0
i
i
Dispersity (Ð) and the Impact on Organic Electronic Devices

Dispersity is a Measure of the Molecular Weight Distribution

Mw
Dispersity of a Polymer: Ð≡
Mn

Because: Mw ≥ Mn , Then: Ð ≥1

Dispersity Can Be Thought of in Terms of the Standard Deviation from the Average:
1
Mw  2
= M n [Ð − 1]
1
σ = Mn  − 1 2

 Mn 

Narrowing the Dispersity (i.e., Minimizing the Standard Deviation in) of the
Polymer Chains, Increases the Ability of the Polymer to Achieve a Higher
Degree of Crystallinity. This, in turn, Increases the Charge Transport Ability of
the Polymer in the Solid State.
 Summary and Preview of the Next Lecture

Organic electronic materials are molecular solids that contain

covalent bonds and are composed mainly of carbon, hydrogen,
and oxygen. They contain a high degree of π-conjugation along
the main chain of the molecules They can form crystalline
domains on the order of millimeters, micrometers, or
nanometers. The structure of the molecule dictates its
optoelectronic properties.

Organic semiconductors The materials can either be small

molecules or polymeric, and they can preferentially transport
holes (p-type) or electrons (n-type). The selection of the
functional groups along the polymer backbone and the degree of
conjugation affect the optoelectronic properties of the material.
Furthermore, side chains generally are used to increase the
solubility of the semiconductor in solution; however, they can
impact the optoelectronic properties as well. The number-
average molecular weight, weight-average molecular weight,
and the dispersity of a polymer can impact the crystallinity and
optoelectronic properties of the materials.

Next Time: The Synthesis of Oft-Used Polymer Semiconductors