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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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In situ poly(3,4-ethylenedioxythiophene) (PEDOT) was the frst example for
PEDOT as synthesized under flm-forming conditions.1

Up to now in situ
PEDOT is the polythiophene with the highest achievable electric conductiv-
ity, although PEDOT:PSS (poly(styrenesulfonate)) is catching up. That is why
in situ PEDOT is of great practical and commercial value. These industrial
aspects are described in Chapters 10 and 11.
This chapter will focus on chemical issues, including some practical advice
for performing oxidative in situ polymerization. There are several investiga-
tions of PEDOT covered by the term in situ in the literature, which deal with
electrochemically synthesized PEDOT layers; these studies are discussed in
Chapter 14. Here the focus is on the preparation of doped PEDOT flms from
EDOT solutions with a chemical oxidant.
The oxidative in situ polymerization is best carried out with ionic oxidants
like iron-III manganese-IV, or similar metal ions in a suitable higher oxida-
tion state. There are various other metal salt oxidants and also completely
distinct compounds, for example, peroxides, suggested for oxidative poly-
merization in the literature or claimed in patents. These alternatives have
been discussed in more detail in Chapter 6. Iron-III is the oxidant preferred
in most experiments in literature and also by far predominant in industrial use.
The solubility requirements for iron-III oxidants are determined by the
limited solubility of EDOT in water in contrast to its miscibility with alcohols
like ethanol or n-butanol in any ratio. So the well alcohol-soluble iron salts of
sulfonic acids are preferred oxidants. Especially p-toluenesulfonate has been
established as a very suitable anion with respect to solubility and reactivity
of the corresponding iron-III salt. Iron-III toluenesulfonate has become the
most widely used oxidant for EDOT in the preparation of in situ PEDOT lay-
ers, scientifcally and commercially.
The overall reaction is described in Figure 8.1. To get a clearer picture,
the equation is drawn for the EDOT hexamer, typically representing every

6911X.indb 91

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92

PEDOT

third thiophene ring as a cationic moiety (of course, this is only one meso-
meric structure).

The overall polymerization reaction can be separated into two steps.
First, the oxidative polymerization of EDOT to the neutral, undoped poly-
thiophene occurs. p-Toluenesulfonic acid and iron-II p-toluenesulfonate are
formed as byproducts stoichiometrically. Therefore two mole equivalents of
Fe-III tosylate are necessary to perform this reaction. In the second step, the
neutral PEDOT is doped by the action of “excess” Fe-III tosylate. As every
third or fourth thiophene moiety loses one electron to form the cationic struc-
ture, about 0.25 to 0.33 additional equivalents of iron(III) toluenesulfonate
are needed for effcient doping. Here also the corresponding stoichiometric
amount of Fe-II tosylate is formed. The third tosylate anion is incorporated
into the polymer structure as the counterion. As the result, the in situ PEDOT
(more exactly, PEDOT:pTs) layers formed by this two-step reaction are ini-
tially containing about 2.3 moles of iron-II tosylate and 2.0 moles of free tolu-
enesulfonic acid. Both can be removed by rinsing with water, for example.
More detailed investigations reveal not only the two-step character of this
reaction, but also an even more complex reaction mechanism. The neutral
PEDOT can be isolated in traces to moderate amounts. For example, using
iron-III chloride instead of the Fe tosylate, which is not suitable for techni-
cal applications due to the formation of corrosive HCl and of deeply colored
tetrachloroferrate counterions, neutral PEDOT can be synthesized in moder-
ate yields.2

The prerequisites necessary for cancelling the reaction before it
comes to complete doping are discussed in more detail in Chapter 6.
Kinetic parameters obtained in a study carried out at Bayer AG explain the
polymerization rate and stoichiometric effects when oxidizing EDOT (see
Figure 8.2).3

The frst step in this reaction is the EDOT oxidation to the cor-
responding radical cation. This is the slowest rate-determining step with a
rate constant k1 = 0.16 L3

mol–3

h–1

(all kinetic parameters given in the following

O

O

S

O

O

S

H

O

O

S

O

O

S

O

O

S

O

O

S

O

O

S

H

6

+

12 FeTos

3

Tos–

Tos–

+

+

– 12 FeTos

2

– 10 TosH

Figure 8.1

In situ PEDOT synthesis.

6911X.indb 92

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The In Situ Polymerization of EDOT to PEDOT

93

description have been determined at 30°C). The free radical cation then very
rapidly dimerizes with k2 = 10 8

–10 9

Lmol–1

h–1

(this parameter is found in lit-

erature4

in accordance to the value for a terthiophene given there and, due to
its magnitude, does not signifcantly infuence the overall reaction rate). End
group oxidation of EDOT oligomers follows, starting with dimer oxidation,
which is remarkably faster than monomer oxidation (k5 = 3 × 103

Lmol–1

h–1
;
the same value as proposed for all chain lengths). Recombination of two
radical cationic end groups results in oligomer formation with the same rate
constant for recombination as for the monomeric cations (k2 = 109

Lmol–1

h–1

).
Finally, oligomers or polymers are doped by further oxidation. Figure 8.2
shows the paramagnetic polaron state as the frst step of doping. This para-
magnetic intermediate step was proved to be plausible by electron spin reso-
nance studies in electrochemical investigations (more details are outlined
in Chapter 14).5–7

The polaron state is then further oxidized to the extremely
stable, highly conductive and diamagnetic bipolaron state of PEDOT.

S

O

O

O

O

S

O

O

S

S+

S

O

O

O

O

O

O

O

O

n

O

O

S

O

O

O–

S

S

S

S

S

O

O

O

O

n

+ Fe(III)

(p-Tos)

3

+ Fe(II)

(p-Tos)

2

O

O

S

CH

HC

O

O

S

HC

O

O

S

O

O

S

CH

n

H+

O

O

S

C

HC

O

S

CH

2

C
H

O

2

O

O

S

HC

2 Fe3+

HC

O

O

S

CH

2

2Fe3+

O

O

S

HC

O

O

S

CH

+ 2 H+

+

2 Fe3+

+ 2H+

O

O

S

CH

C

O

O

S

C

+

O

O

S CH

HC

k

1

k

2

k

5

k

2

k

3

k

4

+

+

+

Figure 8.2

Proposed reaction mechanism for the oxidation of EDOT to PEDOT:pTS.

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94

PEDOT

The intermediate formation of dimeric and trimeric EDOT (see Figure 8.3,
formulae without stereochemical aspects) is a slow equilibrium reaction,8
but does not infuence the overall reaction rate. For the sake of clarity, in
Figure 8.2 the trimer formation has been omitted.
This reaction is a side reaction, so at the end of the overall reaction, the
main yield of PEDOT molecules has been formed via EDOT radical cation
dimerization and a small part via dimer formation. The parameters were
measured independently by experiments with toluenesulfonic acid and
EDOT and the EDOT dimer, respectively. The rate constant k3 for the dimer
formation was found to be 1.5 × 10–3

L2

mol–2

h–1

; the value for the back reac-

tion (k-3) is 1.2 × 10–2

Lmol–1

h–1

. The oxidation rate for the dimer to BEDOT

was determined to 20 Lmol–1

h–1

. Here also, the trimer formation has not been
taken into account; the overall reaction is not infuenced much by the addi-
tional trimer formation. Obviously, all reaction steps in this route to PEDOT
are signifcantly slower than via EDOT radical cation. For a more detailed
discussion of EDOT dimer and trimer formation, see Chapter 5.
The EDOT dimerization was discussed as the reason for a remarkable
catalytic effect of protons on the EDOT oxidation to PEDOT. Addition of
p-toluenesulfonic acid clearly accelerates the overall reaction, but, due to the
aforementioned facts, this cannot be a result of the increased dimer (and
trimer) formation effected thereby.
The best ft of the experimental results with a rate equation including the
accelerating infuence of protons could be achieved with the following equa-
tion for the rate-determining frst step, the oxidation of EDOT to the EDOT+.
radical cation:

r1 = k1 c2

EDOT c2

FeIII

+ k11 cH + cEDOT cFeIII

,

where r is the reaction rate, k is the rate constant, and c is the concentration.
Although this formal kinetic approach does not exactly correspond to the
reaction scheme of Figure 8.2, it is in complete accordance to all experimental
data. k11 has been estimated to 0.026 L2

mol–1

h–1
.

O O

S

O

O

S

O O

S

O O

S

O

O

S

EDOT-Dimer

EDOT-Trimer

Figure 8.3

EDOT dimer and trimer.

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The In Situ Polymerization of EDOT to PEDOT

95

A rather analog adjustment to represent the accelerating infuence of pro-
tons can be made for the oxidation of oligomer end groups:

r5,i = k5 cpolymer(i) cFeIII

+ k51 cH+ cpolymer(i) cFeIII

,

where i is the degree of polymerization. k51 could be determined to 105

L2

mol–2

h–1
.
The activation energy of the rate determining step was estimated to 67 ± 5
kJ/mol derived from an Arrhenius plot of the rate constants k1 at fve differ-
ent temperatures between 10°C and 50°C.
Just when the in situ polymerization of EDOT to PEDOT was established,
most of the pivotal requirements for the preparation of highly conductive
layers already were known to the PEDOT inventors and recorded in sev-
eral patent examples.1

Iron(III)-toluenesulfonate as an optimal oxidant and
lower alcohols (up to butanol) as suitable solvents remained typical compo-
nents in practically used recipes and formulations. Also early investigations
on in situ polymerized PEDOT in the scientifc literature9–11

did not broadly

deviate from the principles disclosed by Jonas, Heywang, et al.1

This did
not change over the years, but several modifcations and improvements have
been made, for example, the addition of imidazole to the EDOT/iron(III)-
tosylate formulation.9,12
A typical recipe for the in situ polymerization is given here in detail.13

1. Chemicals—For the in situ PEDOT layer, the following chemicals are
needed: EDOT; iron(III)-tosylate in n-butanol, typically as a 40%
by weight solution; and imidazole. For the deposition of an adhe-
sion layer on the substrate under the in situ PEDOT layer is needed:
PEDOT:PSS, typically as a 1.3% dispersion in water; or γ-glycidoxy-
propyltrimethoxysilane.

2. Deposition of an adhesion layer on glass substrates—The adhesion layer
is recommended,

especially for the deposition on glass. Without
adhesion layer the in situ PEDOT layers may peel off most probably
during the washing step. The adhesion layer should have a thickness
of 10 to 20 nm.

a. PEDOT:PSS as the adhesion layer—PEDOT:PSS is spin-coated as
a 10 to 20 nm thick flm onto a glass substrate and subsequently
baked at 200°C for about 10 min on a hot plate.

b. γ-Glycidoxypropyltrimethoxysilane as the adhesion layer—γ-Glyci-
doxypropyltrimethoxysilane is spin-coated onto a glass substrate
(1000 rpm, t = 120 sec, Acc. 2, lid closed), or the substrate simply
dipped in diluted epoxysilane solution (0.1 % in isopropanol)
and subsequently dried at 50°C for 5 min in air. Humidity has an
impact on the cross-linking of the epoxysilane. Medium humid-
ity of 30% to 70% is preferred.

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96

PEDOT

3. Mixing the solution—EDOT:iron(III)-tosylate solution (40%):imidazole
are mixed in a weight-ratio of 1:25:0.5. In a frst step imidazole is dis-
solved in the iron(III)-tosylate solution. In a second step EDOT is added.
The mixture can be fltered by using a syringe flter (0.45 µm PVDF).

4. Coating the solution—The solution

has to be processed immediately
after the addition of EDOT. After 5 to 10 min the solution starts to gel
due to polymerization, and the flms will become inhomogeneous.
The solution can be spin coated at spin speeds of 200 to 3000 rpm
and thin homogeneous flms are formed. On a 50 mm × 50 mm large
substrate the flm thickness will be 170 nm at 1000 rpm, t = 30 sec,
Acc. 2, lid closed.

5. Drying the flm—The frst step is 5 min at 50°C on a hot plate in air.
The second step is 60 min at room temperature in air. The air humid-
ity level is 30% to 70%. The flm changes color as EDT polymerizes
while drying.

6. Washing—The flms are washed by shaking the substrate in a beaker
flled with distilled H2O thoroughly to remove Fe salts. Adhering
water is blown off in a N2 fow.

7. Conductivity—The conductivity can be easily checked by printing
two parallel conducting bars (silver paste) on top of the layer and by
using an Ohm meter to determine the resistivity. The conductivity
will typically be in the range of 400 to 600 S/cm.

Another recipe from in the literature shall be given here in a shortened

form14

to give an impression of the substantial similarity of practically all suf-
fcient recipes with small differences to obtain particular effects: A solution
of 6.5 ml iron(III)-tosylate (40% in n-butanol), 2.0 ml water, 0.22 ml EDOT,
and 0.15 ml pyridine was applied by spin coating (250 to 4000 rpm for 30 s)
on to a poly(methyl methacrylate), or PMMA, sheet. Then the PMMA sheet
was baked for 10 min at 65°C. Afterward, the PEDOT layers were washed by
applying 3 ml of a 1:1 mixture of n-butanol and anisole while spinning at 1000
rpm for 20 s, and the washed substrates were further dried for 5 min at 65°C.
In this recipe, water was added to prolong the pot life of the solution and
to decrease the viscosity. The butanol/anisole mixture as a less convenient
washing fuid was utilized to integrate parts of the PEDOT layer into the
plastic substrate (after this procedure the top part of the network consisted
of 30 to 40 vol.% PEDOT and 60 to 70 vol.% PMMA). As a result, very good
mechanical properties and a particular, surprisingly high conductivity of
about 1000 S/cm were found.14
Alternative cerium salt oxidants with limited suitability have been dis-

cussed.15

Whereas cerium-IV sulfate Ce(SO4)2 resulted in reasonable conduc-
tivities, but Ce-contaminated PEDOT, (NH4)2Ce(NO3)6 yielded PEDOT with
only low conductivity. So cerium-based oxidants do not represent advan-
tages compared to iron-III.

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The In Situ Polymerization of EDOT to PEDOT

97

Instead of metal salts, peroxides and other more sophisticated oxidants
were suggested in several publications and patent applications. Rather
closely related to the preferred method for the manufacture of PEDOT:PSS—
the oxidative polymerization with peroxodisulfates—in situ polymerization
by peroxidic compounds has been claimed by several patent applications.16,17
Another patent application utilizes so-called hypervalent iodine compounds
as oxidants.18

Examples for inorganic hypervalent iodine compounds are
iodic acid, sodium iodate (iodine-V), and sodium periodate (iodine-VII).
Typical organic hypervalent iodine compounds19

were of the iodine-III
type, for instance, Koser’s reagent = hydroxy-tosyloxy iodobenzene or
bis(trifuoroacetoxy) iodobenzene (see Figure 8.4).
Several interesting properties may be a motivation for the use of hyper-
valent iodine compounds. For example, EDOT derivatives with thioether
function like 3,4-ethyleneoxythiathiophene cannot be oxidatively polymer-
ized with peroxides due to the oxidation of the thioether function to a sul-
fone group. Use of periodate excludes this reaction and facilitates oxidative
polymerization. Nevertheless, achievable conductivities are only very mod-
erate, and so the practical value is limited.

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