Synthesis and characterization of new adhesion promoter for grafting conducting polymer on oxide substrate

Article abstract of DOI:10.1002/cjoc.201090220

For grafting polypyrrole layers on oxidic substrates, the synthesis and characterization of a new adhesion promoter 11-(pyrrol-3-yl) undecyl trimethoxysilane (PyTMS) were described in this article. The oxidation potential of PyTMS was determined by cyclic voltammetry. The grafting behavior of such an adhesion promoter on oxidized surface and chemical deposition of polypyrrole over the modified oxidized surface were studied. The adsorbed layer on the oxidized substrates thus formed was determined by both contact angle measurements and X-ray photoelectron spectroscopy. Chemical polymerization of terminal pyrrole moieties on such substrates yielded adhesive polypyrrole films, and SEM image showed that the morphology of the polypyrrole films was influenced by the experimental conditions.

Full text of DOI:10.1002/cjoc.201090220

FULL PAPER
Synthesis and Characterization of New Adhesion Promoter for
Grafting Conducting Polymer on Oxide Substrate
,
Cai, Xuediao a,b(蔡雪刁)
Jaehne, Evelinc
Adler, Hans-Juergenc
*
Guo, Wengeb(郭文阁)
a School of Chemistry and Material Science, Shaanxi Normal University, Xi'an, Shaanxi 710062, China
b College of Science, Xi'an Shiyou University, Xi'an, Shaanxi 710065, China
c Institute of Macromolecular Chemistry und Textile Chemistry, Dresden University of Technology,
Mommsenstrasse 4, D-01062 Dresden, Germany
For grafting polypyrrole layers on oxidic substrates, the synthesis and characterization of a new adhesion pro-
moter 11-(pyrrol-3-yl) undecyl trimethoxysilane (PyTMS) were described in this article. The oxidation potential of
PyTMS was determined by cyclic voltammetry. The grafting behavior of such an adhesion promoter on oxidized
surface and chemical deposition of polypyrrole over the modified oxidized surface were studied. The adsorbed layer
on the oxidized substrates thus formed was determined by both contact angle measurements and X-ray photoelec-
tron spectroscopy. Chemical polymerization of terminal pyrrole moieties on such substrates yielded adhesive
polypyrrole films, and SEM image showed that the morphology of the polypyrrole films was influenced by the ex-
perimental conditions.
Keywords adhesion promoter, polypyrrole, oxidic substrate, surface modification
Introduction
mentioned adhesion promoters are 1-substituted pyrrole
organosilane. It was known that 3-substituted pyrrole is
more difficult to synthesize than 1-substituted pyrrole
due to its less stability, that is, 3-substituted pyrrole is
more active. The time to maintain electroactivity of PPy
film formed on 3-substituted modified substrate was
longer than that of PPy film formed on 1-substituted
pyrrole.
In this article, we report for the first time the synthe-
sis of 3-substituted pyrrole organosilane, 11-(pyrrol-3-
yl)undecyl trimethoxysilane (PyTMS), and its use as
adhesion promoters for grafting PPy on oxide substrates
by chemical polymerization. The adsorbed layer of
PyTMS on oxidized substrates was characterized by
various techniques and the chemical deposition of con-
ducting PPy films on such modified substrate was also
studied.
In recent years, conducting polymers have been the
subject of great interest to chemists and physicists.
Polypyrrole (PPy) has been one of the most studied
polymers due to its unique physical and electrical prop-
erties and therefore, has found many applications such
as protection corrosion layers,1 organic electronic de-
vices,2-4 chemical and biological sensor devices,5 etc.
Unfortunately, the performance of such devices is often
limited by the poor adhesion of polypyrrole to device
surfaces.6,7 Organosilanes are an interesting class of
compounds and widely used as an adhesion promoter
between an oxidized surface and a polymeric matrix.8
Up to now, several studies reported on using pyr-
role-functionalized organosilanes to increase the adhe-
sion of the polymers to the substrate. For example,
3-(pyrrol-1-yl) propyl trimethoxylsilane was success-
fully used by Simon et al.9 and Wu et al.10 for adhering
PPy on silicon substrate; Cossement obtained dense and
adhesive PPy films by grafting polypyrrole on the
6-(pyrrol-1-yl)-n-hexyl trichlorosilane modified ITO
electrode;11 Guiseppi-Elie et al.5 and Faverolle et al.12
used other pyrrole-substituted organosilane monolayers
for grafting PPy on SiO2 substrates; Shustak et al.13
used n-alkanoic acid monolayer to promote the adhesion
of polypyrrole on stainless steel. However, all above
Experimental
All chemicals were of reagent grade and obtained
from commercial sources. N-(Triisopropylsilyl)pyrrole
(95%, Aldrich), N-bromosuccinimide (99%, Merck),
butyllithium solution (Fluka, 1.5 mol•L－ in hexane),
1
11-bromo-1-undecene (96%, ABCR), tetra-n-butyl-
ammo-nium fluoride (Fluka, in silica gel), platinum
(0)-1,3-divinyl-1,1,3,3-tetramethyl disiloxane com-
*
E-mail: xdcai@snnu.edu.cn; Tel.: 0086-29-85303508
Received May 20, 2009; revised October 10, 2009; accepted March 5, 2010.
Project supported by Special Research Program 287 (Sonderforschungsbereich, No. SFB 287) of Germany and Scientific Research Plan of Shaanxi
Education Department of China (No. 08JK412).
1272
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2010, 28, 1272— 1278

Synthesis and Characterization of New Adhesion Promoter
plex (solution in xylene, Fluka), trimethoxysilane (95%,
Aldrich), anhydrous magnesium sulfate (99%, Aldrich)
were used as received. Other reagents and solvents were
obtained from Aldrich Chemical Co. The organic sol-
vents were distilled before use.
ter and dried over MgSO4. Removal of the solvent in
vacuo gave a mixture, then column chromatography in
eluting [V(hexane)∶V(ethyl acetate)＝3∶1] gave the
1
pure compound in a yield of 65% (0.3 g). H NMR
(CDCl3, 500 MHz) δ: 8.03 (br s, 1H, H-1), 6.74—6.70
(m, 1H, H-5), 6.60—6.57 (m, 1H, H-2), 6.13—6.10 (m,
1H, H-4), 5.86—5.82 (m, 1H, H-15), 5.04—4.96 (m, 2H,
H-16), 2.58—2.50 (m, 2H, H-6), 2.15—2.07 (m, 2H,
H-14), 1.69—1.59 (m, 2H, H-7), 1.50—1.42 (m, 2H,
H-13), 1.20—1.08 (m, 10H); IR (chloroform) v: 3390
(N—H), 3077 (Arom. C—H), 2926 (CH2), 2856 (CH2),
Synthesis
The synthesis of 11-(pyrrol-3-yl)undecyl trimethox-
ylsilane (PyTMS) was divided to four steps, as shown in
Scheme 1.
－1
Scheme 1 Synthesis of PyTMS
1640 (C＝C), 1463 (Pyrrole ring) cm . Anal. calcd for
C15H25N: C 82.13, H 11.49, N 6.38; found C 82.79, H
10.97, N 6.59.
Synthesis of 11-(pyrrol-3-yl) undecyl trimethoxy-
silane 5 (PyTMS) In a round flask 5 mL of trimeth-
oxysilane and a catalytic amount of 1,3-divinyl-
1,1,3,3-tetramethylsiloxane platinum complex were
added to 0.5 g of ω-(pyrrol-3-yl) undecene 4 in －5—0
℃. The mixture was stirred at this temperature for 1 h,
then warmed to room temperature and stirred overnight.
The excess of trimethoxysilane was removed by evapo-
1
ration and the desired product was got in vacuo. H
NMR (CDCl3, 500 MHz) δ: 8.00 (br s, 1H, H-1), 6.72—
6.69 (m, 1H, H-5), 6.58—6.53 (m, 1H, H-2), 6.10—
6.05 (m, 1H, H-4), 3.55 [s, 9H, (OCH3)], 2.50—2.45 (m,
2H, H-6), 1.59—1.53 (m, 2H, H-7), 1.25—1.18 (m,
18H); 29Si NMR (CDCl3, 500 MHz) δ: －40.08; IR
(chloroform) v: 3396 (N—H), 3090 (Arom. C—H),
2925 (CH2), 2851 (CH2), 1462 (Pyrrole ring), 1191
－ 1
(Si—O—CH3), 880—816 (Si—O—C) cm . Anal.
calcd for C18H35NO3Si: C 63.30, H 10.33, N 4.10; found
C 63.79, H 10.41, N 4.01.
Synthesis of 3-bromo-1-(triisopropylsilyl) pyrrole
Substrates
2
The synthesis of compound 2 was described as
Kozikowski reported.14
p-Doped silicon wafers (Wacker Siltronic AG) sput-
tered with 300 nm TiO2 were cut into pieces (10
mm×10 mm). Silicon wafers (polished to mirror grad,
thermal oxide ca. 4 nm) were also cut into pieces (10
mm×10 mm) and used for determination of PyTMS
layer thickness by ellipsometry.
Synthesis of 3-(undec-10-en-1-yl)-1-(triisoprop－yl-
1
silyl) pyrrole 3
A solution of 1.5 mol•L
n-butyllithium in hexane (13.2 mL, 20 mmol) was
added to a solution of 3-bromo-1-(triisopropylsilyl)-
pyrrole 2 (6.04 g, 20 mmol) in anhydrous THF (80 mL)
at －78 ℃. After 15 min at －78 ℃, 11-bromo-1-
undecene (9.32 g, 40 mmol) was added and after 15 min
the reaction mixture was removed from the cooling bath
and left to room temperature, quenched with 50 mL of
water and extracted with diethyl ether (40 mL×3). The
united extracts were dried (MgSO4) and evaporated in
vacuo. The residue was then purified by column chro-
matography on silica gel using n-pentane to give 4.9 g
of a mixture of desired compound and 1-(triisopropyl-
silyl) pyrrole in a yield of 65%.
Surface modification of substrates with the silane
compounds
Titanium sputtered silicon substrates were first
treated with H2O, 25% NH3 and 30% H2O2 mixture
(2∶1∶1, V/V) at 80 ℃ for 5 s to clean and activate
the surface with more hydroxyl groups. After that, the
substrates were carefully rinsed with distilled water,
dried in an argon stream, and kept overnight in a drying
oven at 50 ℃. Adsorption of the PyTMS onto the sub-
strates was carried out in a glove box by immersing
them into a freshly prepared solution of PyTMS in bi-
cyclohexyl (0.5%, V/V) for 48 h and the physisorbed
silanes on the surfaces were removed by sonication in
chloroform. As-obtained substrates were dried in an
argon flow and stored under argon atmosphere for fur-
ther characterization.
Synthesis of 3-(undec-10-en-1-ly)-1H-pyrrole 4
Tetra-n-butylammonium fluoride (2.5 g in silica gel, 2.7
mmol) was added to a stirred solution of 3-(undec-10-
en-1-yl)-1-(triisopropylsilyl) pyrrole 3 (1.0 g, 2.7 mmol)
in 50 mL of THF. After 5 min at room temperature, the
reaction mixture was filtered, the filtrate was diluted
with ether, and the organic phase was washed with wa-
Chin. J. Chem. 2010, 28, 1272— 1278
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
1273

Cai et al.
FULL PAPER
Chemical deposition of polypyrrole films on silane-
modified substrates
－1
0.1 mol•L Bu4NBF4 as electrolyte.
All experiments were performed at room tempera-
ture in closed Erlenmeyer flasks equipped with a rubber
septum and argon atmosphere, all solvents and solutions
were degassed with argon for 30 min. Polypyrrole films
on PyTMS modified substrates were obtained by oxida-
tive chemical polymerization. The PyTMS-mo－dified
substrates were dipped into 20 mL of a 0.5 mol•L 1 Fe-
ClO4 (oxidant) solution (MeOH/H2O 1∶1, V/V), and
Results and discussion
The synthesis of 3-substituted pyrrole is more diffi-
cult than 1-substituted pyrrole. The interaction of pyr-
role with an electrophilic agent mostly yields
α-substitued products. To function as covalent link be-
tween substrate and polymer layer β-positions of the
pyrrole derivative have to be unsubstituted to allow sur-
face polymerization with additional monomers. A pro-
tection of the pyrrole ring nitrogen with the phenylsul-
fonyl group15 or the bulky tri-isopropylsilyl group14 can
lead to substitution at the β-position. In the first step, the
reaction of 1-triisopropylsilyl pyrrole with N-bromo-
succinimide (NBS) occurred rapidly and gave a mixture
of monobrominated pyrroles.16 Chromatography al-
lowed the isolation of 2 from the reaction mixture in a
79% yield. In the second step, 11-(pyrrol-1-yl triiso-
propyl-3-yl)-1-undecene 3 and 1-triisopropylsilylpyrrole
by-product were obtained on reaction of 11-bromo-1-
undecene with 3-lithio-(triisopropylsilyl)pyrrole.16 This
mixture was conveniently separated by silica gel chro-
matography after desilylation. The removal of the
1-silyl group was easily accomplished with tetra-n-bu-
tylammonium fluoride to give 4 in 65% yield. Finally,
platinum complex catalyzed hydrosilylation of 4 by
trimethoxylsilane resulted in the desired compound 5 in
a good yield. This freshly synthesized compound is a
colorless liquid and with the elapsed time, gradually
becomes dark.
－1
after 5 min 10 mL of 0.1 mol•L solution of pyrrole in
MeOH was injected. The mixture was stirred at room
temperature for 20 h and then the substrate was re-
moved from solution. The sample was washed by soni-
cation three times (10 min each) in methanol first, and
then in water to remove the loosely-adsorbed polymers,
followed by drying with argon.
Physicochemical studies
A drop shape analysis DSA10 apparatus (Krüss
GmbH, Hamburg) was used for contact angle measure-
ments, which were carried out in a static mode with wa-
ter as liquid. The results were averaged from three
measurements at different adsorption time. The XPS
experiments were carried out with a physical Electronic
PHI 5700 ESCA system using a non-monochromatic
Mg Kα X-ray source operating at 300 W with affiliated
PHI software. Spectra were acquired at a base pressure
－8
of 10 Pa. The samples were analyzed at a photoelec-
tron take-off angle of 45° except for the angle-depend-
ent measurements. The detect angle is defined as the
angle between the photoelectron beam and the substrate
surface. For angle-resolved measurements, the detecting
angles of 20°, 45°, 70° and 85° were chosen. Ellip-
sometric studies were performed with a computer inter-
faced DRE GmbH ELX-02C ellipsometer over the
wavelength 623 nm and an incident angle of 70°. The
thicknesses of the silicon oxide overlayer and adsorbed
layer on the silicon substrates were calculated using
ellipsometric parameters and Daf IBM software with the
following settings (single layer mode): air, n0＝1, sili-
con oxide layer, n2 ＝1.458, silicon substrate, ns ＝
3.8600, ks＝0.018 (imaginary part of the refractive in-
dex). A nanoscope dimension 3100 instrument from
Veeco/USA was used for AFM measurements, which
was run in a tapping mode. The thickness of polypyrrole
films was measured with a Dektak surface profile
measuring system. The Raman spectrum was recorded
with a Renishaw Raman Imaging microscope system
2000 equipped with a He-Ne-laser (632.8 nm, 25 mW)
and xyz stage. Cyclic voltrammetric measurements were
carried out in a one-compartment PTFE cell with a
three-electrode configuration using an EC&G 263A
potentiostat/galvanostat. Platinum sheets were used as
working (0.5 cm2) and counter electrodes (3.0 cm2).
Potentials were recorded against an aqueous silver/silver
nitrate reference electrode. All measurements were per-
formed at a scan rate of v＝20 mV/s in acetonitrile with
Figure
1
shows the FTIR spectroscopy of
as-synthesized PyTMS. The charact－eristic bands for
1
methylene stretching－(2928—2855 cm ), pyrro－le C—H
1
1
stretching (3093 cm ), N—H band (3300 cm － ), aro-
1
matic C—C stretching of the pyrr－ole (1500 cm ), and
Si—OMe band (1107, 1079 cm 1) were clearly ob-
served, indicating the formation of PyTMS.
Figure 1 FTIR of as-synthesized PyTMS.
The oxidation potentials of PyTMS and pyrrole were
determined by CV experiments. Figure 2 showed the
CV of these two compounds. It was found that the oxi-
1274
www.cjc.wiley-vch.de
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2010, 28, 1272— 1278

Synthesis and Characterization of New Adhesion Promoter
dation potentials of PyTMS and pyrrole were between
0.5 VAg/Ag＋ and 0.6 VAg/Ag＋, and the oxidation poten-
tials of PyTMS was a slightly lower than that of pyrrole.
As a result, the formation of copolymers of pyrrole and
PyTMS was expected.
layers. At different detector angles the mean free path of
the electrons plays an important role. At low angles
more electrons from the top of the adsorbed layer can be
detected than the deep electrons from the metal oxide
surface. When we chose so-called marker atoms (e.g. N
for top group and Si for substrate attached group) and
followed their ratios, it was possible to get data about
the structure and orientation of the adsorbed layer. Ta-
ble 1 showed the measured intensities of each element
with different detector angles. It was found that the
chemical composition of the adsorbed layer on the tita-
nium surface was far from the theoretical values, which
might suggest that the film was not dense, ordered or
monomolecular. Furthermore, the amount of detected
Ti2p electrons was high, which also indicated the for-
mation of a layer not fully covering the Ti substrate. It
was also worthwhile mentioning that the C/Si and Si/N
ratios for every detector angle showed a quite similar
behaviour: a low detector angles (≤45°), the Si/N in-
tensity ratios decreased with the increase of detector
angle; but at high detector angle, Si/N intensity ratios
increased with the increase of detector angle. The C/Si
ratios increased with the increase of detector angle at a
low detector angle but decreased with the increase of
detector angle at a high angle. These may be due to the
presence of defects, e.g. pinholes and collapse sites, in
the adsorbed layer.
Figure 2 Cyclic voltammetry (CV) curves of PyTMS (solid line)
and pyrrole (dash dot line).
The adsorption of PyTMS can be evidenced by con-
tact angle measurements of titanium substrates treated
with PyTMS for different adsorption time. Compared
with the contact angles of the bare titanium substrate,
significantly increased values after adsorption of
PyTMS were observed. It was also seen that increasing
adsorption time resulted in increasing contact angles,
which could be attributed to the fact that increasing ad-
sorption time led to increasing hydrophobicity. These
observations demonstrated the formation of PyTMS on
the substrate.
The adsorption of the PyTMS molecules on the tita-
nium surface can be further confirmed by angle-re-
solved XPS measurements. Figure 3 shows the corre-
sponding XPS spectra. The peaks of N, C and Si are
clearly observed, indicating PyTMS were adsorbed on
the substrate. The peak of Ti could be assigned to the Ti
substrate used.
Table 1 Angle dependence of the relative atomic concentration
(%) for Ti substrate after modification by PyTMS
Detector
angle/(°)
C1s
N1s O1s Si2p Ti2p
Si/NC/Si
[0.314] [0.499] [0.733] [0.368] [2.077]
20
30
45
60
80
44.6
42.5
41.8
40.0
37.5
2.4
2.5
2.5
2.4
2.2
5.0
36.7
38.3
38.4
39.7
40.9
15.0
8.1
7.5
7.0
6.9
7.1
5.0
8.2 3.37 5.5
9.2 3.0 5.7
10.2 2.80 6.0
11.0 2.90 5.8
12.3 3.23 5.3
Theoretical value 75.0
—
— —
The thickness of the adsorbed layer on Ti can be
further measured by Tougaard nanostructure analysis
during XPS measurement.17 It was found that the thick-
ness (3.12 nm) was bigger than the size of the calculated
PyTMS molecular model (2.26 nm). A similar result
was found for the adsorbed layer on Si substrate (3.41±
0.32 nm) measured by ellipsometry. These observations
confirmed that the adsorbed layer was not a monolayer
but a multilayer.18 Considering that trimethoxysilane
contains three hydrolysable groups, which can react
either with the surface hydroxyls or with each other, it is
expected that the first layer of terminal group (pyrrole
group) with trimethoxysilane group adsorbed on the
surface maybe form H-bond with the second layer of
trimethoxysilane group and therefore, a multilayer is
obtained. Figure 4 showed a schematic illustrating of
the possible structure of as-formed film on the Ti sub-
strate.
Figure 3 XPS of PyTMS on Ti.
Angle-dependent measurements provide further
information about the orientation and order of such
Chin. J. Chem. 2010, 28, 1272— 1278
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
1275

Cai et al.
FULL PAPER
Figure 4 A schematic illustrating of the possible structure of as-formed PyTMS film on the Si substrate.
We investigated the use of as-formed adsorbed layer
as templates for further surface reactions by chemical
deposition of PPy films on the modified substrates. The
chemical surface polymerisation was carried out in a
water/methanol mixture using FeClO4 as both oxidant
and dopant. It was found that the resulting films were
stable against treatment with ultrasonication for at least
20 min in methanol. However, when unmodified sub-
strates were used, only loosely attached particles were
found on the surface, and these particles could be
washed off easily with solvent. The stability of such
films could be further proved with the Scotch tape test,
where no delamination could be observed. These ob-
servations showed that PyTMS-modified substrate ex-
hibited much better adhesion to PPy films than unmodi-
fied substrates.
Figure 5 Raman spectrum of polypyrrole film.
When water was used, a much smoother film with a
thickness of ca. 20 nm was obtained, as shown in Figure
6c. Wu et al. reported that the quality of polymer films
was influenced by the relative permittivity of the solvent
and that solvents with higher relative permittivity would
stabilize the radical cation during the polymerization,
which favored the growth of polymer chains and thus
resulted in the formation of better quality films.10 Water
has high relative permittivity (ε＝78.54) and is a rela-
tively reactive molecule, and PPy films prepared from
aqueous solution showed good adhesion and on the
other hand, had a higher number of structural defects
and a very small thickness. Methanol (ε＝32.63) and
water mixture (2∶1, V/V) as solvent can solve this
problem. Acetonitrile (ε＝37.5) is a good solvent for
electropolymerization, however, polypyrrole films pre-
pared from acetonitile by chemical polymerization had
higher surface roughness. These results are consistent
with other reports.10,20
Raman spectroscopy now is widely used as a valu-
able tool not only for the analysis of the deposition films
but also for the characterization of the doping state and
structural distortions of the conductive polymer skele-
ton.19 We therefore collected the Raman spectrum of
such PPy film measured at 632.8 nm excitation wave-
length, as shown in Figure 5. The peaks between 1600
－1
and 1100 cm region were assigned to C＝C stretch,
C—C stretch, C—N stretch, and C—H bend vibrations,
demonstrating the formation of PPy.
The morphology and the thickness of chemical
deposition of polypyrrole films were examined by SEM
and AFM, respectively, as shown in Figure 6. It was
also found that both the morphology and thickness of
the polypyrrole films deposited on PyTMS-modified
substrates were influenced by polymerization conditions,
such as the solvent and the oxidant used. When acetoni-
trile was used as solvent, a higher rough film with a
thickness of ca. 100 nm was obtained, as shown in Fig-
ure 6a. When hydroxy-containing solvent (such as
methanol/H2O) was used, we obtained a smooth surface
with a thickness of ca. 70 nm, as shown in Figure 6b.
Conclusion
The new adhesion promoter 11-(pyrrol-3-yl) undecyl
1276
www.cjc.wiley-vch.de
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2010, 28, 1272— 1278

Synthesis and Characterization of New Adhesion Promoter
Figure 6 SEM morphology and AFM height images of polypyrrole films prepared in different solvents: (a) acetonitrile; (b) MeOH/H2O;
(c) H2O.
References
trimethoxylsilane (PyTMS) was successfully synthe-
sized. Contact angle measurements showed that an apo-
lar hydrocarbon solvent and long adsorption time re-
sulted in a hydrophobic surface. It was found that the
oxidation potentials for pyrrole and the adhesion pro-
moter PyTMS were very similar and in the range of
0.5—0.6 V. Angle-resolved XPS showed that the ad-
sorbed layer of PyTMS on substrates was not a
monolayer but a multilayer. On these PyTMS-modified
substrates, an adhesive polypyrrole film on PyTMS-
modified substrate was obtained by chemical polymeri-
zation. Both the morphology and thickness of the film
are strongly dependent on the solvent used. Further
work on the control of morphology and thickness and
the determination of the conductivity of the PPy film is
in progress.
1
Wesling, B.; Posdorfer, J. J. Electrochim. Acta 1999, 44,
2139.
2
Burronghes, J. H.; Bradley, D. D. C.; Brown, A. R.; Marks,
R. N.; Mackay, K.; Friend, R. H.; Durns, P. L.; Holmes, A.
B. Nature 1990, 347, 539.
3
4
Dodabalapur, A.; Torsi, L.; Katz, H. E. Science 1995, 268,
270.
Khanduyeve, N.; Senkovskyy, V.; Beryozkina, T.; Bo-
charova, V.; Simon, F.; Nitschke, M.; Stamm, M.;
Grotzschel, R.; Kiriy, A. Macromolecules 2008, 41, 7383.
Guiseppi-Elie, A.; Wilson, A. M.; Tour, J. M.; Brakmann, T.
W.; Zhang, P.; Allera, D. L. Langmuir 1995, 11, 1768.
Qi, Z. G.; Rees, N. G.; Pickup, P. G. Chem. Mater. 1996, 8,
701.
5
6
7
Luzinov, I.; Julthongpiput, D.; Liebmann-Vinson, A.; Greg-
ger, T.; Foster, M. D.; Tsukurk, V. V. Langmuir 2000, 16,
Chin. J. Chem. 2010, 28, 1272— 1278
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
1277

Cai et al.
FULL PAPER
504.
14 Kozikowski, A. P.; Cheng, X.-M. J. Org. Chem. 1984, 49,
3239.
15 Kakushima, M.; Hamel, P.; Frenette, R.; Rokach, J. J. Org.
Chem. 1983, 48, 3214.
16 Bray, B. L.; Mathies, P. H.; Naef, R.; Solas, D. R.; Tidwell,
T. T.; Artis, D. R.; Muchowski, J. M. J. Org. Chem. 1990,
55, 6317.
17 Tougaard, S. Surf. Interface Anal. 1997, 25, 137.
18 Fadeev, A. Y.; McCarthy, T. J. Langmuir 2000, 16, 7268.
19 Furukawa, Y.; Tazawa, S.; Fujii, Y.; Harada, I. Synth. Met.
1988, 24, 329.
8
(a) Willcut, R. J.; McMarthy, R. L. J. Am. Chem. Soc. 1994,
116, 10823.
(b) Sayre, L. N.; Collard, D. M. Langmuir 1997, 13, 714.
Simon, A.; Ricco, A. J.; Wrighton, M. S. J. Am. Chem. Soc.
1982, 104, 2031.
9
10 Wu, C.-G.; Chen, C.-Y. J. Mater. Chem. 1997, 7, 309.
11 Cossement, D.; Plumier, F.; Delhalle, J.; Hevesi, L.;
Mekhalif, Z. Synth. Met. 2003, 138, 529.
12 Faverolle, F.; Attias, A. J.; Bloch, B.; Audebert, P.; Andrieux,
C. P. Chem. Mater. 1998, 10, 740.
13 Shustak, G.; Domb, A. J.; Mandler, D. Langmuir 2006, 22,
5237.
20 Machida, S.; Miyata, S.; Techagumpuch, A. Synth. Met.
1989, 31, 311.
(E0905201 Sun, H.; Fan, Y.)
1278
www.cjc.wiley-vch.de
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2010, 28, 1272— 1278