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We have systematically studied the thin film morphologies of asymmetric polystyreneblock-poly(ethylene oxide) (PS-b-PEO) diblock copolymer subjected to solvent vapors of varying
selectivity for the constituent blocks. Upon a short treatment in neutral or PS-selective vapor,
the film exhibited a highly ordered
array of hexagonally packed, cylindrical microdomains. In the case of
PEO selective vapor annealing, such
ordered cylindrical microdomains
were not obtained. Instead, fractal
patterns on the microscale were
observed and their growth processes
investigated. Furthermore, hierarchical structures could be obtained if
the fractal pattern was exposed to
neutral or PS selective vapor.
Introduction
Block copolymers have attracted significant attention as
nanostructured materials, since they self-assemble into
J. Peng, W. Knoll, D. H. Kim
Max Planck Institute for Polymer Research, Ackermannweg 10,
55128 Mainz, Germany
Y. Han
State Key Laboratory of Polymer Physics and Chemistry,
Changchun Institute of Applied Chemistry, Graduate School of
the Chinese Academy of Sciences, Chinese Academy of Sciences,
Changchun 130022, P. R. China
Fax: 86-431-5262126; E-mail: ychan@ciac.jl.cn
D. H. Kim
Division of Nano Sciences and Department of Chemistry, Ewha
Womans University, 111 Daehyun-Dong, Seodaemun-Gu,
Seoul 120750, Korea
Fax: 82-2-3277-3419; E-mail: dhkim@ewha.ac.kr
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DOI: 10.1002/marc.200700206
Experimental Part
An asymmetric diblock copolymer of PS and PEO, denoted
PS-b-PEO, with a molecular weight of 25 400 g mol1, a polydispersity of 1.05 and a PEO volume fraction of 0.25 was purchased
from Polymer Source, Inc. and used as received. Solutions of the
copolymer (1 wt.-%) in benzene were spin coated onto silicon
substrates. The film thickness was 40 nm determined by a
surface profiler (Tencor P-10, KLA, Tencor). The spin-coated films
were exposed to three different solvent vapors (benzene, toluene,
water) in closed vessels at room temperature (22 8C). In addition,
some samples were also exposed to mixed benzene/water or
toluene/water vapors with an initial volume of 50/50 for comparison. After a certain exposure time, the sample was removed to
an ambient atmosphere.
Atomic force microscopy (AFM) images were obtained in both
height and phase contrast modes using a Digital Instruments
Dimension 3100 scanning force microscope in the tapping mode.
Etched silicon tips on a cantilever (Nanoprobe) with spring constants ranging between 33.2 N m1 and 65.7 N m1 (as specified
by the manufacturer) were used. Optical images were obtained
Macromol. Rapid Commun. 2007, 28, 14221428
2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
(1)
(2)
a)
Benzene
Toluene
Water
PS
0.34
0.35
4.40a)
PEO
0.43
0.54
1.26
www.mrc-journal.de
1423
Figure 1. AFM phase images of PS-b-PEO thin films prepared under different conditions: (a) as-cast
film; (b) annealed in neutral benzene vapor for 10 min; (c) annealed in PS selective toluene vapor
for 5 min; (d) annealed in PEO selective water vapor for 167 h; (e) annealed in mixed toluene/
water vapor for 5 h. Fast Fourier Transform (FFT) pattern in the inset of Figure 1(b) indicates a
perfect hexagonal arrangement of nanocylinders. The phase scale is shown in the inset. Image
sizes are on a 1 mm 1 mm scale.
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DOI: 10.1002/marc.200700206
Figure 2. Optical micrographs in reflection mode for PS-b-PEO thin films after (a) water
vapor annealing for 24 h, removal of water vapor, and storage in air for (b) 48 and (c) 960 h,
respectively. (a), (b) and (c) are AFM height images of PS-b-PEO thin films after (a) water
vapor annealing for 117 h and removal of water vapor, and storage in air for (b) 24 h and (c)
84 h, respectively.
www.mrc-journal.de
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DOI: 10.1002/marc.200700206
(i) What would happen if one put the film with a fractal
pattern into benzene or toluene vapor?
(ii) Can the fractal pattern on the microscale and
cylindrical domains on the nanoscale be combined
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Conclusion
Thin film morphologies of asymmetric PS-b-PEO diblock
copolymer were investigated after annealing by solvent
vapors with neutral and different block selectivity. After
neutral benzene and PS selective toluene vapor annealing,
highly ordered arrays of hexagonally packed cylindrical
PEO domains were produced in a PS matrix. Ordered
cylindrical nanostructures could not be obtained by PEO
selective water vapor annealing, indicating that the
movement of the PS block has a major effect on the
formation of ordered arrays of cylindrical nanodomains.
Mixed benzene/water or toluene/water vapor annealing
proved to be a strategy for manipulating the cylindrical
domain size and the repeat period of the lattice.
It was interesting to observe the development of a
fractal pattern after PEO selective water vapor annealing.
The polymer droplets formed during water vapor act as
nuclei and the anisotropy of the polymer mobility induced
by the water contained in the film plays a critical role in
fractal pattern formation. Further, by exposing the film
with a fractal pattern to benzene or toluene vapor
annealing, hierarchical patterns with well defined cylindrical microdomains could be produced both within and
outside the fractal pattern. Our results open up new
possibilities for the construction of complex controllable
structures by a simple bottom up approach.
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Received: March 18, 2007; Revised: April 27, 2007; Accepted: April
30, 2007; DOI: 10.1002/marc.200700206
Keywords: atomic force microscopy; fractal patterns; hierarchical nanostructures; PS-b-PEO block copolymers; solvent annealing
DOI: 10.1002/marc.200700206