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Effects of thickness on mechanical properties of conducting polythiophene

films

Article  in  Journal of Materials Science Letters · May 2002

DOI: 10.1023/A:1015737106002

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J O U R N A L O F M A T E R I A L S S C I E N C E L E T T E R S 2 1, 2 0 0 2, 715 – 717

Effects of thickness on mechanical properties of conducting

polythiophene films
XI-SHU WANG, XI-QIAO FENG
Department of Engineering Mechanics, Tsinghua University, Beijing 100084, People’s Republic of China
E-mail: xshwang@mail.tsinghua.edu.cn

Owing to the rapid development of conducting poly-
mers [1, 2], it has become possible to control the electri-
cal property of polymers over the range from insulation
to high conductivity. Some polymeric materials have
successively been synthesized with conductivity simi-
lar to such metals as copper [3]. Polymers and electrical
conductivity are no longer mutually exclusive. In addi-
tion, conducting polymers possess some other superior
properties such as low mass density, ease of fabrica-
tion, flexibility in design, and resistance to corrosion.
Therefore, they can be used in various applications as
substitutes of metals [4]. The promise of combining
these properties with good electrical properties in poly-
mers has prompted extensive interest in the last two
decades. However, most of the previously synthesized
conducting polymers are brittle, insoluble, intractable,
and often decomposed before melting [5]. The prepa-
ration of conducting polymers with high strength and
good chemical stability remains still a great challenge.
To date, there is still a lack of investigation on the re-
lationship between the macroscopic properties and mi-
crostructures of conducting polymer films. Recently,
polythiophene thin films with high conductivity and
chemical stability have been synthesized by an electro-
chemical method [6, 7]. The mechanical properties of
such kinds of films are experimentally investigated in
this paper by using an electronic speckle pattern inter-
ferometry method and the SEM technique. Significant
effects of thickness on the strength and Young’s mod-
ulus of films are found.
The conducting polythiophene films used in this
study were synthesized in a one-compartment cell with
the use of an EG&G potentiostat model 283 under com-
puter control [6, 7]. Two AISI 304 stainless steel sheets
with a spacing of 5 mm are used as the working and
counter electrodes. The anodic potential is referred to
the third electrode made of Ag/AgC1. Polythiophene
films were yielded by electrolysis of 0.03 M thiophene
in freshly distilled boron trifluoride diethyl etherate at
a constant potential of 1.3 V. The film thickness was
controlled by adjusting the total charge passed in the
cell. Thus, polythiophene films with different thick-
nesses ranging from one to hundreds of microns were
successively grown/deposited on the base of a stain-
less steel plate by controlling the strength of the elec-
tric current and the synthesis time. These films behave
like metal thin films and can be cut easily into vari-
ous shapes of specimens. An electronic speckle pat-
tern interferometry (ESPI) method [8] was used to
measure the displacement of a film specimen under
strain.
When subjected to an externally applied force, a
polythiophene film may undergo a considerable shape
change, especially in the longitudinal direction due
to the large ratio of the length L to the width W
(L/W ≥ 10). The shape change of a film can be detected
by the ESPI method. Several tensile stress-strain curves
of polythiophene films of different thickness are shown
in Fig. 1. Following the linear elastic deformation, plas-
tic deformation occurs at a threshold stress, referred to
as the yield stress. During plastic deformation, an ev-
ident strain-hardening curve is observed, that is, the
applied stress has to be increased continuously for fur-
ther development of plastic strain. The maximum stress
that a polythiophene film of thickness less than 10 µm
can bear is similar to that of an aluminum thin film.
It can be seen from Fig. 1 that the strength of a poly-
thiophene film exhibits an evident dependence upon its
thickness. As the film thickness increases, the tensile
strength decreases. This size effect of tensile strength is
especially evident when the film thickness is less than
10 µm. However, the film strengths approach to a con-
stant value when the thickness is larger than 15 µm. No
evident difference has been observed in the yield stress
among films when their thickness is larger than about
15 µm. In our measurement, films of thickness 4 µm
possess the highest strength. The physical micromech-
anisms of such a size effect will be analyzed below.
The elastic modulus of a film can also be obtained by
the same experimental system, from which both strain
Figure 1 Stress-strain curves of polythiophene films of different
thickness.

0261–8028 
C 2002 Kluwer Academic Publishers 715

Figure 2 Relationship between Young’s modulus and film thickness.
and stress can be measured with a satisfactory accu-
racy. The Young’s modulus E of conducting polythio-
phene films is plotted in Fig. 2 with respect to the film
thickness. It is seen that the Young’s modulus decreases
rapidly as the thickness increases when the latter is less
than about 10 µm, but approaches to a constant value
for larger thickness. Therefore, the dependence rela-
tionship of the Young’s modulus upon the thickness
includes two regimes, a constant regime for thickness
larger than about 10 µm, and a decreasing regime with
smaller thickness. The main reason of this phenomenon
seems to be associated with the growth mechanisms of
the polythiophene films during electrochemical synthe-
sis. When a film is very thin (e.g., less than 3 µm),
the polythiophene grows in a stable manner on the
base layer of stainless steel, yielding a rather homo-
geneous and compact film with few microdefects. With
its further development, however, more and more big
molecule groups from, causing numerous distributed
microdefects such as micro-cracks and micro-voids in
the whole surface of the film, which can be observed in
SEM images.
To gain a better understanding of the thickness ef-
fects on the mechanical properties of the films, it is
significant to observe their microstructures. The SEM
image in Fig. 3 shows a part of a fracture surface along
the thickness direction of a film after a tensile frac-
ture test, observed at a certain angle from the fracture
surface. It is clearly seen that the cross section of the
Figure 3 SEM image of a fracture surface of a polythiophene film.
716
film includes two regions significantly distinct in mi-
crostructure. A thin film of thickness about 3–4 µm
has a perfect microstructure with few microdefects. As
the thickness increases, more and more defects (voids
and large molecule agglomerates) appear, causing the
degradation and incompact microstructure of the films.
The nucleation and growth mechanism of such a
film can be interpreted by the models in Ref. [9] and
the references therein. The early stage of the electro-
chemical deposition process plays a significant role in
the microstructural morphology and mechanical prop-
erties of the films. In this stage, the polythiophene
molecules ([C4 –H4 –S]n ) deposited on the steel sheet
are relatively small (n is small) and they form in a uni-
form order like crystals. With the further growth of the
film, a three-dimensional deposition of bigger polythio-
phene molecules leads to the incompact microstructure
with profuse defects. At the same time, some salt an-
ionics can be dissociated, as can also be observed in
SEM images.
As a consequence of the synthesis process, the
microstructure of a conducting polythiophene film
changes with the increase in the thickness. The hetero-
geneous microstructure leads to some residual stresses
at the micro scale before and during the desiccation
process of films. Microcracks caused by the hetero-
geneity and the residual stresses can be clearly seen in
SEM images (Fig. 4). However, few microcracks have
been observed in films thinner than 4–5 µm. Microde-
fects seem to be the main reason of the size effects on
the mechanical properties (e.g., strength and stiffness)
of polythiophene thin films under tension. Quantitative
investigation on the property-microstructure relation of
films can be conducted by means of micromechanics
theory, but is omitted in this letter.
In summary, the strength and elastic modulus of con-
ducting polythiophene films synthesized by an electro-
chemical method have been investigated experimen-
tally by the ESPI and SEM techniques. Evident effects
of film thickness on mechanical properties have been
found. High strength and stiffness can be achieved only
in polythiophene films thinner than 10 µm, because the
heterogeneous microstructure causes profuse microde-
fects and residual stresses in thicker films. To obtain
Figure 4 SEM image of microcracks in a conducting polythiophene
film.
 polythiophene films thicker than 10 µm and of higher
quality, the synthesis method needs to be improved to
yield a stable growth of films.
Acknowledgments
The authors wish to thank Prof. Gaoquan Shi’s group
for their help, and gratefully acknowledge the support
from the Basic-Research Foundation of Tsinghua Uni-
versity (JC2000057), and the National Natural Science
Foundation (19891180).
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Received 10 September 2001
and accepted 14 January 2002
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