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Doping in Organic semiconductors

B. In electrochemical doping, the doping charge comes


from an electrode.

Insertion of the anions in


the film
+

B+

A-

B+

B+
A-

Electron transfer= positive doping


E1

Electrode

Electrode

A-

A-

B+
Migration of the cations
In the solvent

Charge injection/extraction (through electrodes)


hole
+

Photogeneration

Abundance of p-type organic semiconductors


Issue is stability with respect to
1. Excess electrons: Most polymers can not withstand
2. Oxygen and water: Acts as p-type dopants

[CH]n + x/2 O2 --> [CH]nx++ + x O2holes

Charge carriers in Organic Semiconductors


Exciton
Not only the holes and
the electrons

Polaron
Soliton

Bi-polaron
Exciton- polaron
.

Exciton
Exciton: Bound electron-hole
pair due to Coulomb interaction

In a solid having a small value of , the positive and negative charges


experience strong attractive forces. On the contrary, in a solid having a large
value of , the positive and negative charges experience relatively weak
attractive forces. Inorganic semiconductors have large values for .

Wannier exciton
(typical of inorganic
semiconductors)

Exciton Bohr radius

Frenkel exciton
(typical of organic
materials)

Dielectric constant of organic semiconductor : 1-3


Inorganic (Si) : 16

Typical Binding energy of Inorganic semiconductors: 10- 100 meV


Binding energy of Organic semiconductors: 100 300 meV (at Room temperature)

Inorganic semiconductor:

wide bands and delocalized states

CB

small exciton
binding energy

Transport gap ~ optical gap

VB

Organic molecular solid


LUMO (EA)

Transport gap

Optical gap

HOMO (IP)
Ground
state
of neutral
molecule

Mater. Horiz., 2014, 1, 1719 | 17

Transport gap optical gap = exciton binding energy

Polarons in organic semiconductors


Self induced Polarization, Lattice distortion
+

Nuclei pulled in
Electrons pushed away

Polarization of the lattice

Lattice of Organic semiconductor is not rigid:


Molecules connected by weak- Vanderwal forces
Inorganic semiconductors have rigid structure:
Atoms connected by strong covalent bonds
Moving electron does not distort lattice
The coupled system of the electron and its associated self-induced polarization/ lattice
distortion is called a polaron

Polarons

Consequences of Polaron formation


Moving electrons have to drag along with the polarization and distortion, thus
slowing down the electrons

Effective mass increases: Polarons are heavier particles than electrons


Mobility reduces
Effect on band gap: Band gap reduces

Combined effect of polaron and exciton on band gap

Measuring transport gap using Direct and


Inverse Photoemission spectroscopy

Ef=Ei + h
Ei=Ef + h

http://arxiv.org/pdf/1001.2330v1.pdf

http://arxiv.org/pdf/1001.2330v1.pdf