A.A. Aal et al. / Electrochimica Acta 56 (2011) 10295–10305
10305
blue with increasing the potential/thickness. In the back-scan,
two reduction peaks were observed. As during oxidation there is
both polymerization and doping the cathodic peaks represent the
reduction of the formerly oxidized polymer. In order to obtain
macroporous PEDOT, a potential of 1.7 V was applied (at room
temperature) to the PS-covered Au working electrode for 1 h. The
electrode was then removed from the glove box and rinsed with
isopropanol to remove the electrolyte. The subsequent removal of
the PS spheres by THF gave the expected macroporous structure of
PEDOT. Fig. 14a shows SEM images of macroporous PEDOT deposits
obtained after applying the desired potential for different periods
of time. As can be seen, the macroporous structure of the polymer
covers a large area which can be seen even on the 40 m × 40 m
scale with individual domains having widths of about 5–7 m.
We also would like to mention that on the same substrate we
observed structures like shown in Fig. 14b, which might be the
result of inhomogenities in the electrical field during the electrode-
position process. A well ordered photonic crystal might require a
geometrically optimized electrochemical cell. Fig. 15 finally shows
photographs of the whole macroporous PEDOT deposit on Au sub-
strate. The deposit gives rise to different colours when changing
the angle of incident light owing to light reflections as has to be
expected for a photonic crystal.
[3] I. Mukhopadhyay, C.L. Aravinda, D. Borissov, W. Freyland, Electrochim. Acta 50
2005) 1275.
(
[
4] G.T. Cheek, W.E. O’Grady, S. Zein El Abedin, E.M. Moustafa, F. Endres, J. Elec-
trochem. Soc. 155 (2008) D91.
[5] F. Endres, S. Zein El Abedin, A.Y. Saad, E.M. Moustafa, N. Borisenko, W.E. Price,
G.G. Wallace, D.R. MacFarlane, P.J. Newman, A. Bund, Phys. Chem. Chem. Phys.
10 (2008) 2189.
[
6] N. Borisenko, A. Ispas, E. Zschippang, Q. Liu, S. Zein El Abedin, A. Bund, F. Endres,
Electrochim. Acta 54 (2009) 1519.
[7] F. Endres, O. Höfft, N. Borisenko, L.H.S. Gasparotto, A. Prowald, R. Al-Salman,
T. Carstens, R. Atkin, A. Bound, S. Zein El Abedin, Phys. Chem. Chem. Phys. 12
(
2010) 1724.
[8] M.V. Fedorov, A.A. Kornyshev, J. Phys. Chem. B 112 (2008) 11868.
[9] R. Atkin, G.G. Warr, J. Phys. Chem. C 111 (2007) 5162.
10] C.A. Zell, W. Freyland, Langmuir 19 (2003) 7445.
11] O. Mann, G.-B. Pan, W. Freyland, Electrochim. Acta 54 (2009) 2487.
12] Y.-Z. Su, Y.-C. Fu, J.-W. Yan, Z.-B. Chen, B.-W. Mao, Angew. Chem. Int. Ed. 48
(2009) 5148.
[
[
[
[
13] B.R. Clare, P.M. Bayley, A.S. Best, M. Forsyth, D.R. MacFarlane, Chem. Commun.
(
2008) 2689.
[
14] S.A. Meiss, M. Rohnke, L. Kienle, S. Zein El Abedin, F. Endres, J. Janek,
ChemPhysChem 8 (2007) 50.
15] Y.B. Xie, C.L. Liu, Plasma Process. Polym. 5 (2008) 239.
16] T. Kaneko, K. Baba, T. Harada, R. Hatakeyama, Plasma Process. Polym. 6 (2009)
[
[
713.
[17] S. Zein El Abedin, A.Y. Saad, H.K. Farag, N. Borisenko, Q.X. Liu, F. Endres, Elec-
trochim. Acta 52 (2007) 2746.
[
18] T.A. Sorenson, T.E. Lister, B.M. Huang, J.L. Stickney, J. Electrochem. Soc. 146
1999) 1019.
[19] M. Alanyalioglu, U. Demir, C. Shannon, J. Electroanal. Chem. 561 (2004)
1.
(
2
[
[
[
20] X. Meng, R. Al-Salman, J. Zhao, N. Borissenko, Y. Li, F. Endres, Angew. Chem. Int.
Ed. 48 (2009) 2703.
21] R. Al-Salman, X. Meng, J. Zhao, Y. Li, U. Kynast, M.M. Lezhnina, F. Endres, Pure
Appl. Chem. 82 (2010) 1673.
22] L.H.S. Gasparotto, A. Prowald, N. Boresinko, S. Zein El Abedin, F. Endres, J. Power
Sources 196 (2011) 2879.
4
. Conclusions
In the present paper we have summarized our recent results on
the interfacial electrochemistry of and electrodeposition from ionic
liquids. We could show that the interface Au(1 1 1)/ionic liquid is a
good candidate for surprises. With [Py1,4]FAP having all impurity
below 10 ppm we see a restructuring of the surface which is dif-
ferent from what we observed in [EMIm]FAP. In a certain potential
regime we see the famous herringbone superstructure of Au(1 1 1)
which we do not see in [EMIm]FAP of the same quality. Furthermore
the interface Au(1 1 1)/[EMIm]FAP reveals slow processes and there
are hints for the adsorption of the cation. The plasmaelectrochem-
ical experiment has shown that germanium nanoparticles can be
made and there are hints for a size dependent colour. Selenium can
be electrodeposited from ionic liquids under environmental con-
ditions at varying temperatures which might have some potential
in an industrial process for the making of CIS solar cells. As will
be shown in a later paper homogeneous layers of different phases
are feasible. Our studies on macroporous materials have shown
that with an alcoholic suspension of polystyrene spheres a vari-
ety of substrates can be easily covered. Especially for the sake of
macroporous electrode materials, e.g. for batteries or materials in
secondary batteries, our process is fast and coating only takes a
few seconds. Macroporous Ag, Al, Si and PEDOT can be made. Even
with almost perfectly arranged PS spheres also the electrochemical
parameters during deposition play a great role. A too fast deposi-
tion rate can corrupt the quality of the PS opal, and the deposition
of 3DOM Si is remarkably difficult.
[23] M. Brettholle, O. Höfft, L. Klarhöfer, S. Mathes, W. Maus-Friedrichs, S. Zein El
Abedin, S. Krischok, J. Janek, F. Endres, Phys. Chem. Chem. Phys. 12 (2010) 1750.
[24] J.V. Barth, H. Brune, G. Ertl, R.J. Behm, Phys. Rev. B 42 (1990) 9307.
[25] Ch. Wöll, S. Chiang, R.J. Wilson, P.H. Lippel, Phys. Rev. B 39 (1989) 7988.
[26] V. Repain, J.M. Berroir, S. Rousset, J. Lecoeur, Appl. Surf. Sci. 162–163 (2000)
30.
[27] H. Oka, K. Sueoka, Jpn. J. Appl. Phys. 44 (2005) 5430.
[28] Y. Hasegawa, Ph. Avouris, Science 258 (1992) 1763.
[29] D.M. Kolb, Prog. Surf. Sci. 51 (1996) 109.
[30] J. Schneider, D.M. Kolb, Surf. Sci. 193 (1988) 579.
[31] N.J. Tao, S.M. Lindsay, Surf. Sci. Lett. 274 (1992) L546.
[32] D.M. Kolb, Andew. Chem. Int. Ed. 40 (2001) 1162.
[33] D.M. Kolb, J. Schneider, Electrochim. Acta 31 (1986) 929.
[34] N. Borisenko, S. Zein El Abedin, F. Endres, J. Phys. Chem. B 110 (2006) 6250.
[
35] R. Atkin, S. Zein El Abedin, L.H.S. Gasparotta, R. Hayes, N. Borisenko, F. Endres,
J. Phys. Chem. C 113 (2009) 13266.
[
36] R. Al-Salman, S. Zein El Abedin, F. Endres, Phys. Chem. Chem. Phys. 10 (2008)
4650.
[37] B.R. Taylor, S.M. Kauzlarich, G.R. Delgado, H.W.H. Lee, Chem. Mater. 11 (1999)
493.
38] R. Gresback, Z. Holman, U. Kortshagen, Appl. Phys. Lett. 91 (2007) 093119.
2
[
[39] H.W. Schock, Appl. Surf. Sci. 92 (1996) 606.
[40] Y. Miyamoto, Jpn. J. Appl. Phys. 19 (1980) 1813.
[
[
[
41] A.K. Graham, H.L. Pinkerton, H.J. Boyd, J. Electrochem. Soc. 106 (1959) 657.
42] C. Uzoh, S. Aksu, US patent 12/642691, 2010.
43] A. Hippel, US Patent no 2,649,409, 1953.
[44] Y. Lai, F. Liu, J. Li, Z. Zhang, Y. Liu, J. Electroanal. Chem. 639 (2010) 187.
[
45] J.H. Kim, M. Chainey, M.S. El-Aasser, J.W. Vanderhoff, J. Polym. Sci. Part A 27
1989) 3187.
(
[
46] M.A. McLaclan, N.P. Johnson, R.M. De La Rue, D.W. McComb, J. Mater. Chem. 14
(2004) 144.
[
[
47] Z. Zhou, X.C. Zhao, Langmuir 20 (2004) 1524.
48] M.-C. Tsai, D.-X. Zhuang, P.-Y. Chen, Electrochim. Acta 55 (2010) 1019.
49] F. Svec, J.M.J. Frechet, Science 273 (1996) 205.
Acknowledgments
50] L. Groenendaal, F. Jonas, D. Freitag, H. Pielartzik, J.R. Reynolds, Adv. Mater. 12
(
2000) 481.
This work was financially supported by the Deutsche
Forschungsgemeinschaft (DFG), the Federal Ministry of Education
and Research (BMBF), the Alexander von Humboldt Association
with a grant to Dr. Aal and EFZN Goslar, Germany (www.efzn.de).
[
[
52] G. Heywang, F. Jonas, Adv. Mater. 4 (1992) 116.
[53] I. Winter, C. Reece, J. Hormes, G. Heywang, F. Jonas, Chem. Phys. 194 (1995)
07.
54] M. Dietrich, J. Heinze, G. Heywang, F. Jonas, J. Electroanal. Chem. 369 (1994)
7.
2
[
8
References
[
[
1] Y. NuLi, J. Yang, P. Wang, Appl. Surf. Sci. 252 (2006) 8086.
2] Z. Feng, Y. NuLi, J. Wang, J. Yang, J. Electrochem. Soc. 135 (2006) C689.