Surfactant-templated Bicontinuous Poly （ 3,4-ethylene dioxythiophene ） (PEDOT) Cubic Phase

Jinghang Wu1 {jinghwu@umich.edu}, Zhangqi Feng2 and David C Martin1,2,3 {milty@umich.edu}

Macromolecular Science and Engineering, University of Michigan, Ann Arbor, MI 481091
Materials Science and Engineering, University of Michigan, Ann Arbor, MI 481092
Materials Science and Egineering, University of Delaware, Newark, DE 197163M

Introduction
Poly （ 3,4-ethylene dioxythiophene ） (PEDOT or PEDT) is a widely water
NP10

used π-conjugated polymer of interest for a number of different

applications1. In this study, PEDOT has been templated into
bicontinuous cubic structures by polymerization within an ordered
surfactant mesophase. These templated PEDOT cubic structures have
nanoscale, interconnected, periodic porous microstructures. This
important for making sensors and actuators with as rapid response 200 µm

times, for facilitating simultaneous electronic and ionic conductivity, and M H L

for controlled drug delivery. The surfactant-templated PEDOT cubic MicellarHexagonal G
Lamellar
phases open windows for precisely controlling the morphology of this Cubic

conjugated, conducting polymer at the nanometer length scale. Monomer

NP10
Aqueous
solution

Experimental LVEM micrograph of PEDOT cubic phases (left: unstained, right: stained with
osmium tetroxide)
A drop of isotropic NP10 was added adjacent to a drop of water or
monomer aqueous solution on a glass slides. The sample was then
covered with cover slip to prevent water evaporation. After the mixture 200 µm

was well mixed by diffusion, the diffusion couples were studied under a H L
M G Ia3d
Nikon Optiphot-2 optical microscope (OM) to map out the phase Micellar HexagonalCubic
Lamellar
diagram. Polarized light

Uv-light exposure
EDOT
Samples were prepared by combining a EDOT-octane solution (up to 200 µm
Ag+
NO3-
10 wt% EDOT), water and TERGITOL® NP-10 non-ionic surfactant in
Oil phase Water phase PEDOT
appropriate proportions to produce bicontinuous cubic phases . The
amount of NP-10, EDOT octane solution and water needed to obtain a
final mixture with cubic symmetry was 55 wt-% NP-10, 22 wt-% octane
Monomer
solution and 23 wt-% DI-water. Four molar times of AgNO3 to EDOT Aqueous
solution
was then added to the mixture after stabilizing overnight. UV-light was
used to facilitate the polymerization. The polymerization process was NP10

monitored by a Rigaku small angle X-ray scattering system (SAXS). M H G L

Micellar HexagonalCubic Lamellar Polarized light
Small clusters of the PEDOT cubic phase were obtained by washing
away all the surfactant and oil in ethanol. A drop of the resulting Diffusion couple of NP10 and water before and after adding monomers
suspension was deposited onto a copper grid with thin carbon films ( Top: NP10 water, middle: NP10 water after adding EDOT, bottom: NP10
and then studied by a 5 kV Delong Low Voltage Electron Microscope water after adding EDOT and bithiophene)
(LVEM). The resulted PEDOT cubic phase was also studied by
Fourier Transform Infrared Spectroscopy (FTIR) to confirm the
existence of PEDOT. Cubi c phas e bef or e and af t er addi ng monomer s

NP10 wi t hout monomer s

Results NP10 wi t h 2. 5% EDOT Before Polymerization After Polymerization
NP10 wi t h 2. 5% EDOT af t er
Pol ymer i z at i on

0 0. 02 0. 04 0. 06 0. 08 0. 1 0. 12 0. 14
q ( 1/ A)

Polymerization Schematics
Molecular structure of NP-10 Small angle X-ray diffraction of NP10 cubic phases before and after polymerization
Conclusions
Index3 Q value(Å-1 ) dhlk (nm)
EDOT monomer was successfully stabilized in cubic phases and PEDOT cubic phase
has been templated by NP-10, water, octane ternary system. SAXS data monitored the
(5 3 2) 0.080 7.85
polymerization process which shows cubic phases were maintained in the process. The
(5 4 3) 0.092 7.00 picture after the polymerization shows dark color which indicates PEDOT formation.
FTIR spectra confirms the PEDOT existence. LVEM images show a regular porous
Calculated d spacing
structure of PEDOT cubic phase with pore size around 7~8 nm. The templated PEDOT
forms clusters about 50-100 nms in size. Current efforts are focused on systems with
increased amounts of EDOT (up to 10 wt% in octane still remain cubic).
FT- I R of PEDOT cubi c phase
C–O–C bond stretching in the References
ethylene dioxy group
Absor bance

1. S. Kirchmeyer, and K. Reuter, Journal of Materials Chemistry, 15, (2005)

Stretching of 2. H. Wang, G. Zhang, S. Feng, Xin. Xie, Colloids and Surfaces A: Physicochem. Eng. Aspects
thiophene ring
256 (2005)
Vibration of
S-C
0 500 1000 1500 2000 2500 3000 3500 4000 4500 3. P.S. Khiew, S. Radiman, N.M. Huang, C.S. Kan and Md. Soot Ahmad, Colloids and Surfaces A:
Wave number ( cm
- 1)
Physicochem. Eng. Aspects 247 (2004)
4. M. A. Khan and S. P. Armes, Langmuir, Vol. 15, No. 10, (1999)

NP-10 Water Phase diagram (The binary phase diagram of NP-10/water: L1, Acknowledgements
micelles; H1, hexagonal phase; V1, cubic phase; La, lamellar phase; L2: reversed
FT-IR spectra of PEDOT cubic phase4 This study was supported in part by the National Science Foundation (NSF) and the ACS Petroleum
micelles) 2
Research Fund (PRF). The authors also would like to thank Bong Sup Shim, Jihua Zhu and Xiaoqian
Ma for their help with the experiments.