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PEDOT Principles and Applications of an Intrinsically Conductive Polymer

PEDOT Principles and Applications of an Intrinsically Conductive Polymer

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Published by: Mario En-tech on Aug 28, 2012
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Ethylenedioxythiophene (EDOT), the monomer for PEDOT, is a transparent liq-
uid. The absorption spectrum of EDOT peaks at 260 nm. The absorption maxi-
mum shifts considerably to lower photon energy when the π system of EDOT is
extended by the formation of dimers and higher oligomers in which conjugation

(b)

100 nm

1

2

3

Agglomerate

Film

(c)

Figure 9.20

(Continued)

6911X.indb 136

10/1/10 8:59:59 PM

PEDOT:PSS

137

is extended to 3 to 6 monomeric EDOT units. This effect has been extensively
studied for EDOT oligomers up to the quater(3,4-ethylenedioxythiophene) in
theory by quantum-chemical calculations72

and experimentally by cyclic volt-

ammetry.73

Besides doping charges, which might generate either radical ions or
dications and yield a signifcant bathochromic shift of the absorption, another
mechanism for a signifcant red shift has been identifed: with protons the neu-
tral oligomers form protonated oligo-EDOT (Figure 9.21).74
The shift anticipated due to the extension of the π system is in accordance
with the model of an electron gas confned to a potential tray. A longer con-
jugation length of the molecule yields a narrower energy gap between the
highest occupied and the lowest unoccupied molecular orbital (HOMO and
LUMO, respectively), an effect which has been observed in many thiophene
systems75–78

and understood based on theoretical molecular orbital calcula-

tions.79

Oligo-EDOTs represent a model system for undisturbed delocalized
π systems due to their almost planar geometry. The rotation between the
thiophene rings is hindered owing to the stabilizing interaction between
oxygen and sulfur atoms of adjacent rings.80,81
Although the absorption spectrum of chemically polymerized PEDOT
may result from various chemical species present, it is a common under-
standing that predominantly the main contribution stems from oxidatively
charged oligomers consisting of 5 to 15 monomeric units.
The absorption of PEDOT:PSS is almost identical to the absorption of in situ
chemically polymerized PEDOT without PSS. Figure 9.22 depicts the relative
transmission, absorption, and refection spectra of CLEVIOS PH 1000 with
5% DMSO added. Strong absorbing features at 193 and 225 nm, not shown
here, are present for pure PSS and PEDOT:PSS.82

These are attributed to π and
π* transitions of the benzene rings in the PSS system. The broad absorption
band in the visible and in the IR region can be interpreted as the contribu-
tion of free charge carriers to absorption or alternatively to excitations of
midgap states (polarons or bipolaron states).82

The addition of additives like
high boiling solvents will not effect the optical properties signifcantly,82
although the conductivity is enhanced by several orders of magnitude (see
Section 9.3). Note that for high-conductive PEDOT:PSS flms the IR refection
can reach 50%.

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