Article

pubs.acs.org/Macromolecules

Control of Morphology in Pattern Directed Dewetting of a Thin

Polymer Bilayer
Sudeshna Roy, Debarati Biswas, Namrata Salunke, Ajit Das, Pavanaphani Vutukuri, Ravdeep Singh,
and Rabibrata Mukherjee*
Department of Chemical Engineering, Indian Institute of Technology, Kharagpur, West Bengal, 721 302, India
*
S Supporting Information

ABSTRACT: We report the dewetting of a thin polymer

bilayer on a low surface energy topographically patterned
substrate with grating geometry. The bilayer, comprising of a
polystyrene (PS) top and poly(methyl methacrylate) (PMMA)
bottom layer was prepared by direct sequential spin coating on
the patterned substrate, using mutually exclusive solvents.
Depending on the coating conditions, three distinct initial
morphologies of the as coated bilayer is possible: type 1, a
discontinuous bottom layer under a discontinuous top layer,
resulting in polymer threads confined within the substrate
grooves; type 2, discontinuous threads of bottom layer
polymer (PMMA) confined within the substrate grooves
under a continuous top layer; type 3, continuous bottom and
top layers. Our experiments reveal that the initial morphology of the film, particularly, that of the bottom layer significantly
influences the final dewetted patterns. For example, in a type 1 or type 2 bilayer the morphology depends significantly on the
relative widths of the PMMA threads (LT−PMMA) and that of the substrate grooves (LP). In case LT−PMMA < LP, the bottom
PMMA layer disintegrates into isolated droplets aligned along substrate grooves, irrespective of the thickness or morphology of
the top PS layer. On the other hand, the overall morphology of the dewetted film is rather strongly influenced by the thickness of
the PS layer and the configuration of the bilayer. In case the PMMA threads span the entire width of the substrate grooves
(LT−PMMA = LP), the droplet formation is suppressed in favor of an intact PMMA thread, with periodic undulations, submerged
under either an undulating thread or an intact layer of PS. In case of a type 3 bilayer, the continuous PMMA bottom layer in
most cases ruptures over the substrate stripes, where it is thinnest. This result in the top PS layer coming in direct contact with
the substrate and subsequently rupture over the same locations, resulting in core shell threads localized over the substrate
grooves. In case of a type 3 bilayer with an ultrathin top film, the two layers rupture simultaneously at different locations and
subsequent dewetting results in an exotic structure comprising alternating array of PS droplets and undulating PMMA threads.
For a thicker bottom layer, the PMMA film is seen to remain intact, over which the PS film dewets, forming undulating threads.
We also construct a morphology phase diagram that depicts the influence of the individual layers on the final dewetted
morphology.

■ INTRODUCTION
Ultrathin polymer films tend to become unstable, sponta-
neously rupture, and dewet on a solid substrate following
variety of mechanisms such as spinodal dewetting engendered
by attractive interfacial van der Waal’s interaction,1−6 sudden
release of residual stresses accumulated due to entanglement of
the long chain molecules during film preparation,7 density
variation, etc.8 Slightly thicker films tend to rupture by
nucleation.4,5,9 A ruptured film subsequently evolves and self-
organizes into variety of meso scale structures such as array of
droplets, holes, bicontinuous patterns etc. due to dewetting.1−9
Any form of film instability is undesirable in applications such
as coatings, adhesives, lubricants, paints, membranes, etc. as
film integrity is essential for these applications.10 However, the
morphological self-organization during dewetting of an unstable
polymer thin film has the potential to become a nonlitho-
graphic technique for engineering meso and nanoscale patterns,
where the feature size and the periodicity of the structures can
be controlled by varying the initial film properties such as the
film thickness (h0) and surface/interfacial tensions.11−36
Typically instability in a homopolymer film is manifested
only when it is heated above the glass transition temperature
(TG) of the polymer or is exposed to its solvent vapor. This
allows additional morphology control of the structures, as the
evolution sequence can be arrested at any intermediate stage by
simply quenching the film to a lower temperature,16 or by
removing it from the solvent chamber. Thus, instability
mediated patterning offers greater flexibility in terms of feature
Received: September 5, 2012
Revised: December 11, 2012
Published: February 4, 2013

© 2013 American Chemical Society 935 dx.doi.org/10.1021/ma3018525 | Macromolecules 2013, 46, 935−948
Macromolecules
size and morphology control, in comparison to the standard
top down lithography methods, where in most cases only a
particular pattern can be created using a specific stamp or a
mask.32
The only limitation of instability mediated patterning
approaches lies in the inherently random nature of the
structures, which hinders their practical utility.1−8 Strategies
have therefore been worked out to align the structures for their
potential use in in fabrication of devices and functional surfaces.
In this regard, dewetting a thin polymer film on a chemi-
cally,11−21 or a topographically patterned substrate12,22−31 is a
promising route, which has been successfully used to align the
instability patterns. Theoretical studies based on nonlinear
simulations,11−14 as well as experiments15−30 have shown that a
perfectly ordered structure on a patterned substrate results only
within a narrow parameter range, which depends on the
commensuration between the natural instability length scale of
the film (λ) and the periodicity of the substrate patterns
(λP).11−16,28 Additionally, on a topographically patterned
substrate, the positioning of the dewetted features can be
tailored by adjusting the nature of the initial adhesion of the
film with the substrate.27,28 A recent work outlines the influence
of substrate feature height on the dewetting dynamics and
pattern morphology.30
Interestingly, most papers on pattern directed dewetting
report the instability of a single layer film.11−31 though
instability and dewetting of thin bilayers comprising of two
immiscible polymers is a fascinating and important prob-
lem.33−65 Bilayers are important in variety of settings including
resist layers in lithography, layered composites, pressure
sensitive adhesive,66 attachment of biological membranes to a
solid surface under liquid etc.67 Instability of a bilayer is
complex as it involves the coupled deformation of multiple,
confined interfaces. This leads to possible creation of exotic
patterns such as submerged, embedded, hollow and core shell
type meso scale structures, which are beyond the fabrication
capability of the standard lithography methods.63−65 In a thin
bilayer, the interaction between the two deformable interfaces
can lead to two distinct short time modes of instability.60−62
When instability is engendered due to a preferential attraction
between the film/film and film/substrate interfaces, an in phase
relative deformation of the two layers result, which is known as
the “bending” mode of deformation. In contrast, when the
instability is triggered due to a preferential attraction between
the film/film and the film/air interfaces, the deformations in the
two layers is out of phase, which is termed as the “squeezing”
mode.60,62 The final dewetted morphology is strongly
influenced by the initial mode as well as the relative growth
rates of instability at the two interfaces.62 Various aspects
related to dewetting of a bilayer, such as the effects of thickness
and viscosity of the individual layers have been investigated,
both based on nonlinear simulations 60−65 and experi-
ments.33−59
Experimentally, dewetting of a polymer bilayer has been
investigated in two distinct configurations. In the first
configuration, dewetting of a thin top layer is studies on a
thick bottom layer which is stable and does not dewet. In this
setting, the problem essentially transforms into dewetting of a
single layer film on a viscous substrate.33−43 where the final
droplet morphology is defined by the Newman configuration,
instead of the customary Young’s configuration which specifies
it on a solid substrate.33,34 The rims formed around ruptured
holes in the top layer often penetrate into the softened bottom
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Article
layer, reducing the dewetting velocity significantly.36 In the
second experimental configuration, both layers are thin and
therefore become unstable, either simultaneously or sequen-
tially, resulting in complex structures.44−59 In this case, the final
dewetted morphology depends largely on the initial instability
mode. de Silva et al. have experimentally shown a distinct
stability transition between the two layers depending on the
ratio of individual film thickness in an unstable PS (bottom)/
PMMA (top) bilayer coated on a silicon (substrate).52 They
argued that a thin PMMA film on a thick PS film is destabilized
due to dispersion forces, in contrast to a thin PS film below a
thick PMMA film which undergoes spinodal dewetting due to
long-range forces.52 Xu et al. have recently showed that in a
PMMA/PS bilayer on an oxide coated silicon substrate, the
evolution starts with a strong deformation at the film/air
interface over a nondeforming film/film interface when the
bottom PMMA layer is very thin. In contrast, a rapid
deformation at the film/film interface is observed when the
PMMA layer is thick and has lower viscosity.58 Also irregular
and faceted structures form due to anisotropic growth of the
holes, due to strong viscous dissipation in a high viscosity, low
thickness PS top layer, which is associated with significant
interfacial slippage between the two layers.59
Interestingly, dewetting of a thin bilayer on a heterogeneous
substrate has received far less attention,68−72 in comparison to
both pattern directed dewetting of a single layer film,11−31 and
dewetting of a thin polymer bilayer on a flat substrate,33−65
probably due to complex experimental protocol involving large
number of parameters. We must highlight that a variety of
ordered structures with complex morphologies such as core
shell columns, hierarchical and enclosed cage like structures etc.
have been successfully created by applying an externally applied
electric filed across a thin polymer bilayer.66−71 Regarding
dewetting of a bilayer on a patterned substrate, based on long
wave nonlinear simulations, Sharma et al. have predicted the
morphology of a dewetted thin bilayer on topographically and
chemically patterned substrates, and have identified conditions
under which ordered structures can be obtained.73,74 Their
prediction show the formation of parallel stripes of the
constituent polymers of the bottom and top layers along the
grooves and ridges of the substrate from the dewetting of a
bilayer on grating substrate with high γS. In contrast, on a low γS
grating, the top layer ruptures sequentially after the bottom
layer has ruptured, forming ordered encapsulated patterns.73,74
Very recently, Ding and co-workers have experimentally studied
the dewetting of a thin PS film coated on a topographically
patterned thick PMMA substrate.75−77 The morphological
evolution proceeds with the disintegration of the PS layer into
stripes and threads aligned along the PMMA ridges and grooves
respectively, that subsequently rupture into aligned small and
large droplets.75 The kinetics of film rupture depends on the
viscosity of the two layers and is governed by the more viscous
component.72 For a thick and continuous PS top layer, the
dynamics is also strongly influenced by the molecular weight of
the layer.77 They have also reported the vertical pattern decay
and lateral in-phase capillary breakup of a nano imprinted
polymer bilayer, where a complex ‘‘in-phase’’ capillary breakup
of the PS stripes on the PMMA substrate ridge eventually
results in strings of PS ellipsoids aligned orthogonal to the
imprinting direction. At later stages, these ellipsoids anisotropi-
cally coalesce into thick threads before disintegrating into
droplets due to Rayleigh instability.76,86
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Macromolecules
It becomes evident from the preceding discussion that
dewetting of a thin polymer bilayer on a topographically
patterned substrate appears to be a fascinating problem which
has never been experimentally investigated. In this article, we
report the dewetting of a thin polymer bilayer comprising of a
PS top and a PMMA bottom layer, on a grating substrate made
of low surface energy cross-linked PDMS. The bilayers were
prepared by direct sequential spin coating on the topo-
graphically patterned substrate using mutually exclusive
solvents. It is well-known that depending on the coating
condition a continuous or a discontinuous film may result on a
topographically patterned substrate.78 We identify three distinct
possible initial morphologies of the bilayer film on the grating
substrate, which are as follows: type 1, a discontinuous bottom
layer under a discontinuous top layer, resulting in bilayer
threads confined within the substrate grooves; type 2, a
discontinuous thread of the bottom layer polymer within the
substrate grooves, buried under a continuous top layer; type 3,
both layers continuous. By varying the thickness of the two
layers independently, we show that it becomes possible to
create complex ordered structures, such as aligned array of core
shell droplets, undulating multilayer ribbons and laterally
coexisting ordered structures of both PS and PMMA. We
also construct a morphology phase diagram that shows the
influence of each layer independently on the final dewetted
morphology. Our experiments reveal that both morphology and
periodicity of the dewetted structures are strongly influenced by
the dewetted PMMA bottom layer.
■ EXPERIMENTAL DETAILS
The grating substrates were soft lithographically fabricated on ∼5 μm
thick Sylagrad 184 (a two part cross-linkable poly(dimethylsiloxane)
(PDMS); Dow Corning, USA) films. The concentration ratio of
oligomer (part A) to cross-linker (part B) was maintained at 10:1 (v/
v) in the PDMS composition. Dilute Sylgard 184 solution in n-hexane
(SRL, India) was spin coated on cleaned double side polished quartz
pieces (15 mm ×15 mm, Applied optics, India). The Sylgard 184 films
were cured for 12 h at 120 °C for complete cross-linking. The cross-
linked films were subsequently kept immersed in n-hexane for 15 h for
removal of the un-cross-linked oligomer molecules.79 Subsequent to
solvent wash, the films were dried at 60 °C for 6 h in a vacuum oven.
The dried samples were subsequently patterned by a pressure-less
room temperature imprinting technique, using flexible patterned
metallic foils peeled from commercially available CD discs as
stamps.80,81 The imprinted patterns were made permanent by
exposing the film while in contact with the stamp to UV−ozone
exposure, which oxidizes the cross-linked PDMS film surface with the
formation of a stiff oxide layer.80,82 The foils are porous,81 which
allows the atomic oxygen and ozone to reach the PDMS film surface
and oxidize. The oxide layer also acts as a diffusion barrier during spin
coating as well as during selective solvent washing, and does not allow
the solvent to penetrate the into PDMS matrix. Details about the
patterning methodology can be found elsewhere.80,81 The periodicity
(λP), substrate groove width (LP) and the stripe height (HS) of the
patterned substrates were measured using an AFM (Agilent
Technologies, USA Model 5100) and are 1.5 μm, 750 and 120 nm,
respectively. Patterned PDMS substrates were preferred owing to their
low cost and ease of fabrication. Similar substrates have also been used
in several recent dewetting related studies.26−28,30 It is important to
highlight that though Toluene is a good solvent for PDMS, it does not
swell the PDMS substrate during spin coating, primarily due to the
presence of the thin impermeable silicon oxide crust on the PDMS
substrate.78 That there is no swelling of a cross-linked PDMS substrate
during spin coating of a polymer on it has been highlighted in several
recent publications.66,78,82
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Article
The bilayer samples were prepared by sequential spin coating (Apex
Instruments, India) of PMMA (MW: 305 K, Sigma, U.K.) and PS
(MW: 280 K, Sigma, U.K.) from their dilute solutions in HPLC grade
Toluene and 1-chloropentane (synthesis grade, Merck India)
respectively, on the patterned substrates. The drop volume, rpm,
and spinning durations were 200 μL, 2500, and 1 min respectively, for
both the layers. After coating each layer, the films were air-dried for 3 h
followed by annealing in an air oven at 60 °C for 6 h to remove any
remnant solvent. The morphology of the as cast PMMA bottom layer
and that of the bilayers coated on the patterned substrates were
investigated using an AFM in intermittent contact mode with a silicon
cantilever (PPP-NCL, Nanosensors Inc. USA). Dewetting of the
bilayer films was triggered by thermally annealing the films in a
vacuum oven at 130 °C, a temperature that is higher than the TG of
both the polymers. Samples were withdrawn from the oven after every
30 min to observe the progressive morphological evolution using an
AFM.
To investigate the deformation at the polymer/polymer interface, it
was necessary to preferentially remove the top PS layer, which was
accomplished by washing the samples with 1-chloropentane for 2 h,
followed by drying under vacuum for 6 h at 60 °C. It is worth pointing
out that the UVO exposed patterned cross-linked Sylgard 184
substrate does not swell during the selective washing step with
chloropentane, which is discussed in details in section S2 of the
Supporting Information. For removing the PMMA layer, which was
necessary only in certain cases, the samples were washed in acetic acid
for 10 min followed by washing in deionized water and drying in a
vacuum oven for 6 h.
Further, it is well-known that a film directly spin coated on a
topographically patterned substrate is either discontinuous or has an
undulating top surface and therefore there is no simple way to define
its exact thickness (h).78,83 Consequently, for such a film we define an
equivalent film thickness (hE), which corresponds to the thickness of a
film coated under identical conditions (same cn and rpm) on a flat
substrate of the same material.78 The thickness of the flat films are
measured using a variable angle imaging ellipsometer (Accuron
GmbH, Model: EP3SW, 532 nm laser source). The effective thickness
of the different bottom (hE‑PMMA) and the top (hE‑PS) layer films used
in the present study are listed in Table 1.
Table 1. Details of the As Cast Films
The equilibrium contact angles of toluene and 1 − chloropentane
on the patterned cross-linked Sylgard 184 substrates ware measured
using a contact angle goniometer (make: Ramé-Hart, USA, Model
290) and were found to be ∼35° and 32° respectively. This implies
that the cross-linked Sylgard 184 substrate is partially wetted by the
solvent used for coating both the layers. It was also observed that a
PMMA film was fully wetted by 1-chloropentane. Further, we
calculated the surface energy of the substrate, γS‑sub = 24.2 mJ/m2
from Owen’s equation, using water, ethylene glycol, and toluene as
probing liquids.84
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Macromolecules Article

Figure 1. (A) Morphology of an as cast bilayer comprising hE−PMMA = 11.1 nm and hE−PS = 12.8 nm. Inset A1 shows cross sectional line scan of the
bilayer threads as well as the PMMA under layer thread. Inset A2 shows the existence of gap between the bilayer thread and the confining substrate
groove walls. (B) Undulating threads observed after 2 h of annealing. (C) Disintegration of the undulating threads into droplets after 4 h of
annealing. (D) Final dewetted morphology comprising array of aligned droplets after 5.5 h of annealing. (E) Array of PMMA droplets after
preferential removal of the PS layer. AFM line scans show the core shell nature of each droplet.

■ RESULTS AND DISCUSSION

For cn−PMMA ≤ 1.0%, a discontinuous bottom layer comprising
isolated polymer threads or strips confined within the substrate
grooves results due to insitu dewetting of the polymer solution
during spin coating.78 At even lower concentrations the
polymer threads do not span the entire width of the substrate
grooves. For example, when cn‑PMMA ≈ 0.25% with correspond-
ing hE−PMMA = 11.1 nm, the width of the PMMA threads
LT−PMMA is ≈340 nm, which is narrower than the width of the
substrate groove (LP = 750 nm). In this specific case, the height
of the PMMA thread is hT−PMMA ≈ 28 nm. At higher cn−PMMA,
the isolated threads span the entire width of the substrate
groove (LT−PMMA = LP), which is observed in films with
hE−PMMA =19.1 and 38.3 nm. For cn‑PMMA ≥ 1.5%, a continuous
PMMA film results, with an undulating top surface. The
amplitude of the surface undulations (aS‑PMMA) progressively
reduces with increase in cn‑PMMA, vis−a−vis hE−PMMA. As the
substrate is partially wetted by toluene, the undulations on a
continuous PMMA film surface are 180° out of phase with
respect to the substrate patterns.78 In cases where a continuous
PS film is coated on a discontinuous PMMA film (type 2
bilayer), the surface undulations on the PS film are also 180°
out of phase with respect to the substrate pattern, due to partial
wettability of cross-linked PDMS substrate by the solvent, 1−
Chloropentane. A continuous film is therefore thinnest over the
938
substrate stripes, where the local thickness is denoted by hL.
From measured values of hE and as, we estimate hL following a
simple calculation procedure discussed in the Supporting
Information. On the other hand, as 1-chloropentane fully
wets PMMA, the surface undulations of the two layers are in
phase with each other, when the top PS film is coated on a
continuous PMMA bottom layer.
The values of spreading coefficients (SPS−Sub = −24.2 mJ/m2,
SPMMA−Sub = −24.8 mJ/m2 and SPS−PMMA = 2.7 mJ/m2)
calculated based on the individual surface energies (γS) of the
two constituent polymers (γPMMA = 41.8 mJ/m2, γPS = 38.3 mJ/
m2),85 that of the substrate (γS‑sub = 24.2 mJ/m2), and the
interfacial energies between them (γPMMA−PS = 1.2 mJ/m2,
γPMMA−Sub = 3.8 mJ/m2 and γPS−Sub = 6.1 mJ/m2) shows that
the PMMA bottom layer is unstable on the substrate (negative
SPMMA−Sub). A PS layer is stable on a continuous PMMA
(positive SPS−PMMA) layer but becomes unstable when it comes
in direct contact with the PDMS substrate (negative SPS−Sub).
With this background, we now discuss the dewetting and
morphological evolution of PS−PMMA bilayers with 8
different thickness combinations on a grating substrate.
Additional experiments were also performed, with different
thickness combination of the two layers, which have been used
to formulate a morphology phase diagram shown in Figure 9.
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Macromolecules Article

Figure 2. (A) Morphology of an as cast bilayer comprising hE−PMMA = 11.1 nm and hE−PS = 41.8 nm. Inset A1 shows cross sectional line scan of the
bilayer threads as well as the PMMA under layer thread. (B) Undulating threads observed after 2.5 h of annealing. The overall dewetted morphology
remains nearly identical with further annealing. (C and D) Morphology of the PMMA under layer after 2.5 and 5.5 h of annealing, respectively,
showing a transition from undulating threads to isolated PMMA droplet array.

Figure 3. (A) Partially dewetted morphology of a bilayer comprising of hE−PMMA = 11.1 nm bottom layer and hE−PS = 41.8 nm top layer, after 30 min
of annealing. The continuous PS film has started to rupture over the substrate stripes. Inset A1 schematically shows the cross section of the bilayer,
which comprises of a discontinuous bottom layer (LT−PMMA < LP), buried under a continuous top layer. Inset A2 shows the as cast morphology of
the bilayer. (B) Final dewetted morphology of the film comprising undulating threads observed after 5.5 h of annealing. (C) Array of dewetted
PMMA droplets aligned along the substrate grooves, formed under the undulating threads, observed after removing the top PS layer, from the
structure shown in part B.

The discussion is organized in terms of progressively
increasing bottom layer thickness (hE−PMMA). The first five
case studies involve a discontinuous bottom layer. Out of them,
in the first four cases (Figures 1−4) hE−PMMA = 11.1 nm, which
implies that LT−PMMA < LP. The next example (Figure 5)
involves a discontinuous bottom layer (hE−PMMA = 38.3 nm),
but the threads span the entire width of the substrate (LT−PMMA
= LP). It is worth pointing out that though only one example of
this specific case is shown, the final dewetted morphology is
rather generic and is observed in bilayers with different
thickness ratios, which can be seen in Figure 9. The last three
examples involve bilayers with a continuous bottom layer film,
939
involving hE−PMMA =73.3 and 138.9 nm films (Figures 6-8). For
every thickness combination; experiments were performed with
at least four identical samples prepared in different batches, and
AFM scans were performed at five locations for each sample, to
check the reproducibility of the results and to strengthen the
error bars in Figures 9 and 10.
Dewetting of Bilayers with Discontinuous Bottom
Layer. First, we discuss the instability in a type 1 bilayer,
comprising of a hE‑PS = 12.8 nm top and a hE‑PMMA = 11.1 nm
bottom layer. The cross-sectional profiles of the PMMA and
the PS threads and the contours of the confining substrate
groove walls is shown in the form of a superimposed AFM line
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Macromolecules Article

A2 of Figure 1A. The first signature of instability in the bilayer

Figure 4. (A) Array of dewetted PMMA droplets under an intact PS
film observed after 24 h of annealing in a bilayer comprising of
hE−PMMA = 11.1 nm bottom layer and hE−PS = 123.7 nm top layer. The
morphology of the dewetted film attains this form after 6 h of
annealing and does not change subsequently. Inset A1 schematically
shows the cross section of the type 1 bilayer, where (LT−PMMA < LP).
Inset A2 shows the as cast morphology of the bilayer film. Inset A3
shows the phase contrast image of the sample after 24 h of annealing.
(B) Array of aligned PMMA droplets formed under the intact PS film,
observed after removing the top layer.
scan (inset A1 of Figure 1A), which shows that the as cast
bilayer is discontinuous, comprising of isolated bilayer threads
with thread width LT−B ≈ 530 nm and thread height hTB ≈ 37
nm. In this specific case not only LT−PMMA < LP, but even the
width of the bilayer threads are narrower than that of the
substrate groove (LT−B < LP). Consequently there is a clear gap
between the as cast bilayer threads and the confining substrate
walls on both sides of each thread, which can be seen in inset
threads appears after ∼2 h of thermal annealing, which is in the
form of alternating narrower and wider domains along each
thread (Figure 1B). The relatively long time required for the
onset of instability is attributed to the high molecular weight of
both the polymers, which makes the dynamics sluggish. The
undulations appear due to the well-known Rayleigh−plateau
instability,86 engendered by the cross-sectional curvature of the
long polymer threads. The amplitude of the undulations grow
with time, as Laplace pressure drives flow of liquid from the
narrower zones of the threads to wider, bulgy zones.
The periodicity of the undulations along the axial direction of
the thread is measured to be λA ≈ 1.21 ± 0.081 μm. On the
basis of linear stability analysis (LSA), the characteristic
wavelength (λA) of capillary instability in an infinitely long
liquid thread of width LT is λA = 4LT.70,85,86 On the basis of
LT−B ≈ 530 nm, the calculated value of λA ≈ 2.2 μm, which is
much higher than the experimentally obtained value of λA
≈1.21 μm. However, if the same calculation is performed based
on the width of the inner PMMA thread (LT‑PMMA ≈ 340 nm),
then λA turns out to be ≈1.36 μm, which is close to the
experimentally observed value of λA. On the basis of the fact
that λA exhibits the scaling with LT−PMMA rather than LT−B, we
argue that the undulations appear in the inner PMMA threads
first and the outer PS thread simply deforms along the contours
of the under layer. It can also be argued that since the inner
PMMA thread has a lower radius compared to the bilayer
threads, the magnitude of the Laplace pressure in the inner
PMMA thread is higher, leading to its preferential rupture.

Figure 5. (A) Morphology of a type 2 bilayer comprising of hE−PMMA = 38.3 nm bottom layer and hE−PS = 59.8 nm top layer, after 30 min of
annealing. The continuous PS film is seen to rupture over the substrate stripes. Inset A1 schematically shows the cross section of the bilayer, which
comprises of a discontinuous bottom layer that covers the entire width of the substrate groove (LT−PMMA=LP), buried under a continuous top layer.
Inset A2 shows the as cast morphology of the bilayer. (B) Polymer thread localized over the substrate grooves after 1.5 h of annealing. (C) Final
dewetted morphology comprising undulating threads observed after 5.5 h of annealing. The morphology did not change any further with longer
annealing. (D) PMMA threads with periodic undulations aligned along the substrate grooves, observed after removing the PS layer, from the
structure shown in part C.

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Macromolecules Article

Figure 6. (A) Morphology of a type 3 bilayer comprising of hE−PMMA =73.3 nm bottom layer and hE−PS =19.4 nm top layer, after 1 h of annealing.
The image shows rupture of the PMMA film as well as that in the PS film (at some locations) over the substrate stripes. (B) Mildly undulating
bilayer threads localized over the substrate grooves after 5.5 h of annealing. (C) Undulating PMMA threads, after preferential removal of the PS from
the structure shown in part B. (D) Schematic representation of the dewetting mechanism.

Figure 7. (A) Dewetted morphology comprising undulating PMMA threads over substrate grooves and array of PS droplets over the substrate
stripes, in a type 3 bilayer comprising of hE−PMMA =73.3 nm bottom layer and hE−PS = 12.8 nm top layer, after 5 h of annealing. (B) and (C): Fully
dewetted morphology after Preferential removal of PS and PMMA, which shows undulating PMMA threads along substrate grooves and aligned PS
droplets over substrate stripes, respectively. (D) Schematic representation of the mechanism of dewetting.

With time the inner PMMA threads disintegrate into aligned
isolated droplets, buried under undulating, still intact PS
threads. As the PMMA threads break down into droplets, the
PS threads now come in direct contact with the base of the
substrate grooves at the locations where the PMMA threads
have snapped off. As a PS film is also unstable on a low γS
PDMS substrate, the PS threads also start to break up at the
same locations with progressive annealing for approximately 4
h, resulting in isolated droplets (Figure 1C). Initially the
droplets are slightly elongated, which eventually take a more
941
spherical shape, leading to minimization of surface energy. The
final dewetted morphology, which appears after 5.5 h of
annealing and does not change subsequently, comprises of a
highly ordered and periodic array of nearly equal sized droplets
aligned along the substrate grooves (Figure 1D). The
periodicity of the droplets along the direction of the stripes is
λD‑B ≈1.184 ± 0.112 μm, which is close to the value of λA of the
undulating threads before their disintegration into droplets.
The droplet diameter (dD‑B) is ≈750 nm, which seems to be
governed by the width of the substrate grooves (LP). As the
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Macromolecules
Figure 8. (A) Nucleated holes in a hE−PS = 19.4 nm thick top PS layer
over an bottom layer of hE−PMMA =138.9 nm, after 1 h of annealing.
(B) Dewetting of the PS film over the PMMA humps, with growth of
holes after 3 h of annealing. (C) Final dewetted morphology
comprising undulating PS threads confined within the valleys on the
surface of an intact PMMA bottom layer, after 6 h of annealing. (D)
Schematic representation of the dewetting mechanism.
droplets form due to disintegration of a bilayer thread, it is
obvious that they possess a composite structure comprising
both PS and PMMA. To understand the precise nature of each
droplet, the PS layer was preferentially removed. This reveals
the structure of the dewetted PMMA threads, which also
comprises of an array of aligned droplets along substrate
grooves. However, the PMMA droplets are smaller in diameter
Figure 9. Morphology phase diagram as a function of the individual layer thicknesses. The solid symbols represent the overall morphology of the
dewetted bilayer and the open symbols represent the same for the dewetted bottom layer only. Inset A and B shows the morphologies of the
dewetted bilayer and the bottom layers separately. Symbols have following meaning: (■, □): droplet array; (●, ○): undulating threads; (▼, ▽):
Intact layers; (▲): undulating or dewetted PS layer. The demarcating lines act as guides only.
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(dD−PMMA ≈ 543 ± 7 nm) as compared to the bilayer droplets,
though their periodicity (λD‑PMMA ≈ 1.221 ± 0.162 μm) is
nearly the same as λD‑B. Thus, it can be argued that each
composite droplet resulting from the dewetting of the bilayer
threads has a core shell structure, which can be seen in the
superimposed AFM line scan shown as inset E1 of Figure 1E.
In the next three cases (Figures 2−4), we investigate how the
thickness of the top layer (hE−PS) influences the overall
morphology of the dewetted structures, when the bottom layer
configuration remains unaltered (hE‑PMMA = 11.1 nm). When
hE‑PS = 41.8 nm, the as cast morphology of the bilayer is again
type 1 (Figure 2A). However, it can be seen from the
superimposed AFM line scans (inset A1 to Figure 2A), that
unlike the previous case, where LT−B < LP, here the isolated
bilayer threads span the entire width of the substrate grooves
(LT−B = LP). As LT−PMMA is ≈340 nm, the gap between the
PMMA thread and the substrate groove walls are entirely filled
up by PS.
For this bilayer, the first sign of instability is observed after
2.5 h of annealing, which is in the form of periodic undulations
along the threads (Figure 2B). Interestingly, in this case with
progressive annealing the stripes do not decay into droplets and
the overall morphology remains nearly unaltered as that seen in
Figure 2B, even after annealing the samples for 36 h. For an
undulating thread to decay into droplets, liquid from the
thinner zones of the thread has to physically flow to the wider
areas. However, as the entire substrate groove is filled with
polymer, therefore the space required for the growth of the
bulges along the substrate stripe is not available, which in turn
hinders the decay of the threads into droplets. In fact, we will
see that in many subsequent cases a similar mechanism is
responsible for suppression of droplet formation. The
periodicity of the undulations is λA ≈ 1.39 ± 0.211 μm,
which is close to the value of λA observed in the previous case
as well as the theoretically predicted value of λA based on
LSA,86,87 which implies that similar to the previous case, the
Rayleigh instability first sets in along the inner PMMA thread.
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Macromolecules Article

Figure 10. (A) Variation of structure periodicity λA (droplet/undulating threads) along the stripes as a function of bottom layer thickness (hE−PMMA).
Inset A1 shows variation of the feature periodicity of the bottom layer λB as a function of hE−PMMA. The demarcation boundaries of the three zones
act as guides only. A11, B21, B22, C21, C22 are the schematic morphologies of the bilayers in the respective zones. (B) Variation of feature
periodicity λA as a function of total effective thickness of the bilayer (hE−T). Different symbols represent different bottom layer thickness: 11.1 nm
(■), 19.1 nm (●), 28.7 nm (▲), 38.3 nm (▼), 48.7 nm (◊), 59.4 nm (solid triangle pointing left) and 73.3 nm (solid triangle pointing right).

At this point it is important to note that though the substrate
grooves are entire filled up by the bilayer threads (LT−B = LP),
the inner PMMA threads do not span the entire substrate width
(LT−PMMA < LP) and therefore the confining substrate groove
walls do not impose any restriction on the growth of the
undulations along the PMMA threads. This allows the inner
PMMA threads to eventually decay into isolated droplets,
under continuous, undulating PS threads. The progressive
morphological evolution of the submerged PMMA threads with
time can be seen in Figures 2C and 2D, where the top PS layer
has been preferentially removed. Figure 2C shows undulating
PMMA threads after 2.5 h of annealing, which shows an
undulating PMMA thread. In Figure 2D, the undulating
PMMA thread has disintegrated into an well-ordered array of
PMMA droplets after 5.5 h of annealing, though the undulating
bilayer threads remain intact. The λD‑PMMA and dD−PMMA of the
droplets are measured to be ≈1.256 ± 0.113 μm and ≈593.2 ±
3 nm respectively, which are close to that observed in the
previous case, though the overall morphology of the dewetted
bilayer is distinctly different in the two cases.
In Figure 3, we present the dewetting scenario of a type 2
bilayer comprising of a hE‑PS = 59.8 nm film coated on a hE‑PMMA
= 11.1 nm bottom layer. The undulation amplitude of the
continuous top PS layer aS−PS = 23.8 nm and hL−PS ≈ 5 nm
(inset A2, Figure 3A). The morphology of the bilayer is
schematically shown in inset A1 of Figure 3A. After 30 min of
annealing, the top layer preferentially ruptures over each
substrate stripe (Figure 3A), where the continuous PS film is
thinnest and the destabilizing van der waal’s interaction
between the film/air and film/substrate interfaces is strongest.
After rupture, the three phase contact line (air−PS−substrate)
retracts rapidly, revealing the top of the substrate stripes and
localizing the polymer as isolated bilayer threads over the
substrate grooves (Figure 3A). At this stage, the morphology of
the partially dewetted film largely resembles the as cast
morphology of the bilayer discussed in Figure 2. However,
between the two cases, there is a difference in the location
where the bilayer threads make the three phase contact line
with the patterned substrate. In the earlier case with hE‑PS = 41.4
nm (inset A1 of Figure 2A), the bilayer threads form the
contact line along the side walls of the substrate grooves. The
lateral confinement imposed by the substrate groove walls
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prevent any overflow of liquid over the top of the substrate
stripes when the threads become undulating, which is seen in
Figure 2B. In contrast, in the latter case, as the bilayer threads
form due to initial rupture and dewetting of the top layer, a
continuous contact line is formed over the top of the substrate
stripes, close to the edges. This allows the liquid to overflow
over the top of the stripes, when the thread become undulating,
as seen in Figure 3B. The phenomena of thread undulations
impinging over the substrate stripes are rather generic and
observed in many type 2 bilayers with different thickness
combinations. The threads attain their final undulating
morphology after about 5.5 h of annealing (Figure 3B). The
periodicity of the undulations is λA ≈ 1.273 ± 0.029 μm, which
is close to λA observed in the previous two cases. Preferential
removal of the PS top layer reveals an aligned array of PMMA
droplets (Figure 3C), which is morphologically similar to that
observed in the previous two cases, with near identical values of
λD‑PMMA (≈ 1.186 ± 0.135 μm) and dD−PMMA (≈ 564.6 ± 6
nm). We argue that in this case also the submerged PMMA
threads disintegrating into isolated droplets due to Rayleigh
instability. Also, similar to the previous case, lack of space
within the substrate grooves prevents the decay of the
undulating PS threads into droplets. Thus, dewetting in this
case results in complex morphology comprising an array of
PMMA droplets below well-ordered undulating PS threads,
aligned over each substrate groove. The two sequential
instability modes associated with the dewetting process, that
is rupture of the continuous PS films over substrate stripes and
disintegration of the PMMA threads into droplets, have
distinctly different time scales, with the latter being significantly
slower than the former. This is evident from Figure 3A, which
shows isolated threads without any undulation in the early
stages of dewetting. This implies that the instability in the
PMMA threads set in later after the PS film has ruptured and
the isolated bilayer threads have formed.
Figure 4 shows the dewetted morphology of a type 2 bilayer
comprising hE‑PMMA = 11.1 nm under a thick continuous PS
layer having hE‑PS =123.7 nm, with aS = 6.8 nm and hL−PS ≈ 65
nm (inset A2, Figure 4A). The indicative morphology of the
system is schematically shown as inset A1 of Figure 4A. Unlike
in the previous case, where a low hL−PS (<10 nm) engenders
preferential rupture of the film over each substrate stripe, in the
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Macromolecules
present case the PS film is found to remain stable without
rupturing, even after 24 h of annealing. However, similar to the
earlier three cases, the submerged PMMA threads disintegrate
into aligned droplets, due to Rayleigh instability. The array of
submerged droplets under an intact PS film can be seen in
Figure 4A. The intactness of the top PS layer is confirmed from
the phase contrast AFM image shown in the inset A3 of Figure
4A, which shows a low phase contrast of ≈7° only. Preferential
removal of the PS film reveals the PMMA droplet array, with
λD‑PMMA ≈ 1.129 ± 0.109 μm and dD−PMMA ≈ 549.3 ± 4 nm.
The values of dD−PMMA and λD‑PMMA in all the four examples
discussed so fare are nearly the same, which implies that in all
the cases the PMMA threads disintegrate into droplets
following the same mechanism, irrespective of the thickness
or morphology of the top layer. Consequently, the morphology
of the dewetted bottom layer is also identical in all cases (array
of PMMA droplets) irrespective of the overall morphology of
the dewetted films, which depends on the thickness of the top
layer.
Next we move on to discuss the instability of another type of
bilayer that also contains a discontinuous bottom layer, but the
PMMA threads cover the entire width of the substrate (LT‑PMMA
= LP). This type of bottom layer morphology is observed for
hE‑PMMA = 19.1 and 38.3 nm. In Figure 5, we capture the
dewetting sequence of a type 2 bilayer with a continuous top
layer (hE‑PS= 41.4 nm), on a bottom layer with hE‑PMMA = 38.3
nm. In this case, aS =24.4 nm, and the calculated hL−PS ≈ 8 nm
(inset A2, Figure 5A). After annealing for 30 min, the PS film
preferentially ruptures over each substrate stripe (Figure 5A),
following a mechanism identical to that observed in Figure 3A.
Subsequent retraction of the three phase contact line over the
top of the substrate stripes leads to localized bilayer polymer
threads along the substrate grooves (Figure 5B). Subsequent
annealing results in the onset of Rayleight Instability along the
threads, rendering them undulating (Figure 5C).71,80,82 At this
stage, the overall morphology of the dewetted bilayer closely
resembles Figure 3B. However, a clear distinction between the
two cases becomes evident when the top PS layer is removed.
Unlike all the earlier examples, where the bottom PMMA layer
decays into droplets, in the present case the droplet formation
in the PMMA threads is suppressed, resulting in undulating
PMMA threads along each substrate groove. It may be pointed
out that the periodicity of the undulating bilayer threads is λA ≈
1.413 ± 0.161 μm and that of the submerged undulating
PMMA threads is λA‑PMMA ≈ 1.502 ± 0.101 μm, which implies
that λA ≈ λA‑PMMA. The suppression of droplet formation in the
PMMA threads is attributed to the fact that LT‑PMMA = LP. We
have already discussed in the context of Figure 2 that for an
undulating thread to decay into droplets, it is necessary that the
amplitude of the undulations grow, which requires flow of
liquid from the thinner zones of the undulating thread to the
thicker, bulgy areas. However, in this case, as LT‑PMMA = LP,
there is no place for the bulges along the PMMA threads to
grow, and therefore the threads fail to decay in to droplets.
Consequently, the overall morphology of the dewetted bilayer
comprises of multilayer undulating threads aligned along
substrate grooves.
At this point, one might argue that as the substrate grooves
are entirely filled with polymer, why at all the Rayleigh
Instability sets in. To explain this, we would like to highlight
that the cross section of each thread is convex and therefore
limited gap is available between the upper portion of the thread
and the substrate grooves.30 Rayleigh instability sets in over this
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area of each thread, leading to the undulations. It is further
observed that λA‑PMMA does not scale as 4 times LT‑PMMA any
more. In fact it turns out to that the observed value of of
λA‑PMMA is approximately half of that expected from linear
stability analysis.71,80 We argue the change in the scaling
between λA‑PMMA and LT‑PMMA is also related to the suppression
of growth of Rayleigh Instability in the threads. As the
instability amplitude fails to grow due to confinement by the
substrate walls, the liquid from two adjacent growing bulges
flows back toward the portion of the thread joining the two, an
area which is supposed to narrow down to enable the growth of
Rayleigh instability. However, as this section now receives
excess liquid from two adjacent bulges, instead of thinning
down this section has local accumulation of liquid, which results
in an additional bulge along the thread. Thus, the observed
λA‑PMMA appears to be approximately half of that expected from
Rayleigh instability. The formation of an undulating bottom
layer is rather generic, as it is seen in all bilayers with a
discontinuous bottom layer, having LT‑PMMA = LP. The overall
morphology is also similar in most cases, comprising multilayer
undulating threads except when the top PS layer is very thick,
which does not dewet at all (as seen in case of Figure 4).
Dewetting of Films with Continuous Bottom Layer.
We now focus our attention on dewetting of bilayers with
continuous PMMA bottom layer. As 1-chloropentane fully wets
PMMA the PS top layer in such cases is always continuous,
resulting in type 3 bilayers. Figure 6 shows the dewetting of a
bilayer comprising of a hE−PS = 19.4 nm top and hE‑PMMA =73.3
nm bottom layer. For the bottom layer, aS−PMMA = 21.2 nm,
which leads to a value of hL−PMMA ≈ 8.0 nm. The amplitude of
the surface undulation reduces to aS−B = 17.4 nm, once the PS
top layer is coated. This implies that the PS film is slightly
thicker over the grooves on the PMMA film and thinner over
the PMMA humps, as is schematically shown in frame D1 of
Figure 6D. The onset of instability in this bilayer is observed
with rupture of the PMMA film over each substrate stripe,
where the bottom layer is thinnest. This results in retraction of
the PMMA meniscus over the substrate stripes. Concurrently,
the PS film comes in direct contact with the substrate over each
stripe, where the PMMA film has ruptured. As the PS film is
also unstable on the substrate (negative SPS−Sub), the PS layer
also ruptures over the substrate stripes. The sequential rupture
of the PMMA and the PS film is observed after about 1 h of
annealing and can be seen in Figure 6A. The inset to the figure
clearly shows that over some of the stripes both the films have
ruptured and over the other stripes only the PMMA film has
ruptured under an intact, PS film. With time, the film retracts
over the substrate stripes, localizing the polymer as bilayer
threads above the substrate grooves, which is seen in Figure 6B.
Preferential removal of the PS layer reveals the underlying
undulating PMMA threads (Figure 6C, after 5 h of annealing).
The sequential rupture mechanism is schematically shown in
Figure 6D. It may be noted that in this specific case the
undulations in the threads (both the layers) are neither very
prominent, nor periodic, as compared to examples shown
before. We must admit that we are unable to resolve this issue
fully. The formation of multilayer threads from dewetting of a
type 3 bilayer on a low γS grating substrate matches
theoretically predicted morphologies by Bandyopadhyay and
Sharma rather well.68 Similar evolution sequence is also
observed when hE−PS = 41.8 and 59.8 nm, on a hE‑PMMA
=73.3 nm bottom layer. A hE−PS = 123.7 nm thick film remains
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Macromolecules
stable on the disintegrated PMMA film, forming aligned
PMMA threads under an intact PS film.
Figure 7 shows the dewetting of another type 3 bilayer where
hE−PS = 12.8 nm and hE‑PMMA = 73.3 nm. In this case, aS−B =
13.3 nm (<aS−PMMA), from which it can be calculated that the
local thickness of the PS layer over the PMMA humps is ≈7
nm. In contrast to the previous case, where a sequential rupture
of the two layers is observed, in this case the two layers ruptures
almost simultaneously at two different locations, upon
annealing. While the PMMA film ruptures as usual over each
substrate stripe, the PS film ruptures over each PMMA hump,
where it is thinnest. Based on a positive value of SPS−PMMA, a PS
layer over a PMMA layer should be stable. However, we feel
that the rupture of the PS layer above the PMMA layer is due
to nucleation, as at these locations the local thickness of the PS
film is lowest. Additionally, as the PMMA film ruptures over the
substrate stripes (where it is thinnest) and dewets, the PMMA
meniscus retracts back, leading to accumulation of more
PMMA on the existing bulges over the substrate grooves. This
accumulation is associated with an increase in the height of the
PMMA humps. This in turn results in vertical flow of PMMA
over the substrate stripes. This flow imparts an additional stress
on the PS film at the PS−PMMA interface above each PMMA
hump, which further facilities rupture of the PS layer.
Subsequent reorganization leads to the formation of alternate
threads of PMMA and PS over the substrate grooves and
substrate stripes, respectively. The mechanism is schematically
shown in Figure 7D. With progressive annealing, both sets of
threads become unstable due to Rayleigh instability. While the
PS threads decay into isolated droplets aligned over the
substrate stripes, the PMMA threads exhibit periodic
undulations inside the substrate grooves, which can be seen
in Figure 7A. From the AFM image of the final dewetted
structure, it is however not possible to conclude that the
droplets and the undulating threads are of PS and PMMA
respectively. To verify this, the individual polymers were
removed following protocol described in the Experimental
Section. Figure 7B shows the morphology after preferential
removal of PS, which confirms that the undulating threads are
made of PMMA. In contrast, preferential removal of PMMA
threads leads to a structure that comprises of polymer droplets
arranged over the substrate stripes (Figure 7C), which verifies
that the droplets are composed of PS. The overall dewetted
morphology obtained in this case (Figure 7A) is a rare example
where aligned patterns of two different materials coexist
simultaneously on the same surface, which has been reported
for the first time, to the best of our knowledge. The ability to
generate multi material ordered structures is beyond the
capability of any existing lithography or instability mediated
patterning methods. This opens up possibility of fabricating of
multi functional surfaces. We would like to highlight that this
unique morphology was observed only in this specific bilayer
configuration, though across several samples.
Figure 8 shows the dewetting of a type 3 bilayer comprising
of a thick hE‑PMMA = 138.9 nm bottom layer and a thin hE‑PS =
19.4 nm. The as coated bottom layer has surface undulations
with aS−PMMA = 8.2 nm. Calculations show that in this case
hL−PMMA ≈ 70 nm, which is fairly high and therefore, unlike the
previous two cases the PMMA layer does not preferentially
rupture over the substrate stripes. In fact, the bottom remains
stable even after annealing for 36 h. The amplitude of the
bilayer film, after coating the PS layer is aS−B = 4.8 nm. Similar
to the previous cases, the PS layer is thinnest over the PMMA
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humps. Upon annealing for approximately 1 h, the PS film
ruptures over each PMMA hump, with the appearance of
nucleated holes (Figure 8A). This observation is surprising, as
SPS−PMMA = 2.7 mJ/m2 is positive and therefore a PS film
should be stable on a PMMA film. However, we feel that in this
case, as well as in the previous example the ultrathin PS film
ruptures over an intact PMMA layer due to defect sensitive
nucleation,6 which is further facilitated due to a low positive
value of the spreading coefficient. The signature of heteroge-
neous nucleation is very clearly seen in Figure 8A. With
progressive annealing, the holes grow in size, the PS film dewets
the top of the PMMA humps and flows into the valleys on the
PMMA film surface, forming isolated PS threads. The growth
of holes and formation of the PS threads can be seen in Figure
8B, after 3 h of annealing. While majority of the PS drains in to
the PMMA valley, some PS threads disintegrate over the
PMMA humps forming tiny PS droplets. With time, the PS
threads exhibit axial undulations due to Rayleigh instability.
The final dewetted structures thus comprises of isolated,
undulated PS threads aligned along the valleys of an intact
PMMA film, along with some tiny PS droplets over the PMMA
humps. The mechanism of the dewetting process is schemati-
cally shown in Figure 8D. Inset C1 of Figure 8C shows the
morphology of the film after preferential removal of PS, which
is nearly identical to the morphology of the as cast PMMA film
on the substrate, confirming that the PMMA layer does not
dewet and the undulating threads as well as the tiny droplets
are constituted of PS. In contrast, preferential removal of
PMMA results in a morphology which resembles the substrate
(inset C2, Figure 8C). This shows that the PS layer does not
come in direct contact with the substrate and therefore,
removing the PMMA layer entirely removes the PS structures
formed above it, revealing the bare substrate.
■ DISCUSSION
From the preceding discussion, we note that a variety of
ordered structures result due to dewetting of thin polymer
bilayers on topographically patterned substrates. The final
morphology depends on host of factors, most important being
the individual layer thickness (hE−PS and hE−PMMA), in addition
to the initial morphology of the bilayer. Aiming toward a
deeper understanding on how the equivalent thickness (hE) of
each layer influences the final dewetted structures, we present a
morphology phase diagram in Figure 9. The figure is
constructed by compiling the final dewetted morphology of
all the bilayers investigated as a part of this study. A complete
list of all the bilayers investigated with different hE−PMMA and
hE−PS combinations is available in Table S3 of the Supporting
Information. In addition to the morphology of the dewetted
bilayers, Figure 9 also includes the morphology of the dewetted
bottom layer for every thickness combination. The individual
morphology landscape of the dewetted bilayer and the
dewetted bottom layers, shown separately in insets A and B
of the figure respectively, allow us to understand precisely the
morphological transitions as a function of the thickness of the
two layers. To facilitate discussion, we also show the variation
of periodicity of the dewetted features (periodicity of the
droplets, or that of the undulating threads λA) along the
substrate stripes as a function of the bottom layer (hE−PMMA)
and the total bilayer thickness (hE−T) in Figures 10A and 10B
respectively. The inset to Figure 10A shows the variation of
structure periodicity of the dewetted bottom layer only (λB) as
a function of hE−PMMA.
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Macromolecules
From inset B of Figure 9, it becomes evident that the
morphology of the dewetted bottom layer remains largely
independent of the top layer thickness (hE−PS). Further, the
dewetted bottom layer morphology can be classified into three
distinct categories: category B1, array of aligned droplets,
observed for hE−PMMA = 11.1 nm; category B2, undulating
aligned ribbons confined within/along the substrate grooves,
observed for hE−PMMA = 19.1−73.3 nm; category B3, stable
bottom layer, observed for hE−PMMA = 98.5 and 138.9 nm. On
the basis of this observation, we divide the morphology phase
diagram in inset B, Figure 9 into three distinct zones (B1, B2,
and B3), which correspond to the three regimes mentioned
above. The diagram shows the existence of two critical bottom
layer thickness: hE−PMMA−C1, at which the morphology changes
from droplet array to undulating threads (zone 1 to zone2), and
hE−PMMA−C2, which marks the transition from zone 2 to zone 3.
Our experiments reveal that hE−PMMA−C1 lies between 11.1 and
19.4 nm, and hE−PMMA−C2 between 73.3 and 98.5 nm, but could
not be determined more accurately. The demarcating lines
between different zones in the figures are added as guides for
easy understanding. Interestingly the lower boundary of zone 1
does not extend all the way to hE−PMMA = 0, as the threads
break down in to droplets during spin coating for very low
polymer concentrations.78 We found that it is difficult to obtain
isolated PMMA threads along the substrate grooves once
cn−PMMA is <0.20%, which corresponds to hE−PMMA ≈ 9 nm.
Below this concentration, droplets start forming due to spin
dewetting. Such cases have not been included in our study, as
strictly speaking, coating a top layer above a droplet array does
not qualify as a bilayer.
Inset A1 to Figure 10A reveals two fascinating aspects about
the dewetting of the bottom layer. First, we observe that λB
does not increase monotonically with hE−PMMA, something that
is routinely observed in dewetting over a flat substrate. Second,
the periodicity of the bottom layer patterns (λB) is found to be
independent of the top layer thickness (hE−PS). The second
observation endorses that the bottom layer becomes unstable
under an intact top layer, in all cases irrespective of hE−PS. In
case the top layer, ruptured before or along the bottom layer, it
would have resulted in the PMMA layer coming in direct
contact with air. This would have led to a significant increase in
the interfacial tension of PMMA, from 1.2 mJ/m2 (γPS−PMMA)
under an intact PS layer to 41.8 mJ/m2 in air (γPMMA), which in
turn would have surely resulted in a change in λB depending
whether the bottom layer was dewetting under an intact or a
ruptured top layer. In that case, a thin PS top layer would have
ruptured faster than a thicker top layer and therefore it was
likely that a PMMA layer dewetting under a thin top layer
might have come in contact with air. This would have invariably
resulted in a higher λB. However, as that does not happen and
λB remains independent of hE−PS, we therefore conclude that
the bottom PMMA layer always remains submerged under PS
during dewetting. It should be noted that in certain cases (such
as Figures 3 and 5) where the PS layer ruptures before the
bottom PMMA layer, the PS film actually ruptures and dewets
over the substrate, while the PMMA threads are still
submerged.
The second observation, that λB does not increase
monotonically with hE−PMMA is attributed to the geometry of
the system. We have already seen in Figures 1−4 that for very
low hE−PMMA, the PMMA threads do not span the entire width
of the substrate grooves (LT−PMMA < LP), which is shown in the
schematic B11 in Figure 10A. With increase in hE−PMMA, the
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discontinuous PMMA threads span the entire width of the
substrate (LT−PMMA = LP), which is seen in films with hE−PMMA
= 19.1, 28.7, 38.3, and 48.7 nm (zone B2). In this regime,
increase in hE−PMMA effectively results in greater extent of
groove filling, while the thread width remains constant. This is
schematically shown in insets B21 and B22 of Figure 10A. With
further increase in hE−PMMA, the bottom layer becomes
continuous with very low aS−PMMA over the substrate stripes.
Such bottom layers rupture over the substrate stripes and
PMMA retracts back over the substrate grooves. However, in
this case the width of the PMMA thread becomes higher than
the width of the substrate groove (LT−PMMA > LP). In this
regime, L T−PMMA progressively increases with h E−PMMA
(schematically shown in insets B31 and B32) until aS−PMMA
becomes high enough and the bottom layer does not rupture
any further. It has already been discussed that the PMMA
threads, irrespective of their origin disintegrates due to Rayleigh
instability, where the periodicity of the features depends on the
width of the threads. As the width of the PMMA threads
(LT−PMMA) remain constant within the zone B2, therefore the
undulation periodicity (λB) also remain constant in this zone
and does not increase monotonically with increase in hE−PMMA,
which has been captured in inset A1 of Figure 10A. It can also
be seen that the nature and magnitude of variation of λA and λB
with hE−PMMA is nearly identical, which suggests that the overall
instability length scale of the bilayer is strongly influenced by
the instability of the bottom layer. This argument is further
strengthened from Figure 10B, which shows the variation of λA
with the total bilayer thickness (hT). It can be clearly seen that
λA does not exhibit any systematic variation with hT. In the
figure, points with same hE−PMMA are shown with the same
symbol, which again verifies the strong dependence of λA on
hE−PMMA.
Similar to the morphological demarcation in inset B of Figure
9, we also demarcate the morphology landscape of the bilayer
in inset A of Figure 9. Zone A1 corresponds to a morphology
comprising of an ordered array of dewetted core shell droplets,
which is seen in Figure 1. Zone A2 corresponds to undulating
threads aligned along the substrate grooves. These undulating
PS threads can rest either on PMMA droplets (Figures 2−4) or
undulating PMMA threads (Figures 5 and 6). Zone A3 refers to
an interesting scenario, where an ultrathin top PS layer dewets
on a stable bottom layer. We have discussed earlier that the
value of the spreading coefficient, SPS−PMMA = 2.7 mJ/m2, which
implies that a PS layer is stable on a PMMA film. However, the
magnitude of SPS−PMMA is very low. Thus, in ultrathin PS films
the surface fluctuations at the free surface of the PS film may
grow due to nucleation, resulting in dewetting of the PS film on
an intact PMMA layer, which is observed in Figures 7 and 8.
With increase in PS film thickness, the possibility of nucleative
rupture of the PS layer diminishes and the top layer becomes
stable, which falls under zone A4. However, zone A4 refers to
an intact top layer, which can be either on an intact bottom
layer (right portion of zone A4) or over a disintegrated PMMA
layer (left portion of zone A4). In the left part of zone A4, the
PS film is in periodically varying contact with both PMMA
threads and the top of the substrate stripes. Even though
SPS−Sub is negative, when the PS layer thickness over the top of
the substrate stripes becomes adequately thick, the PS layer
does not rupture at all which is seen in Figure 4.
dx.doi.org/10.1021/ma3018525 | Macromolecules 2013, 46, 935−948
Macromolecules
■
CONCLUSION
In this article, we have investigated the dewetting and pattern
formation of a thin polymer bilayer on a low γS, topographically
patterned substrate. We observe that the initial morphology of
the films, particularly whether the bottom layer is continuous or
discontinuous, significantly influences the final dewetted
patterns, as well as the evolution sequence. Even when the
bottom (PMMA) layer is discontinuous, the dewetted
morphology is strongly influenced by the relative widths of
the PMMA threads (LT−PMMA) and the substrate groove (LP).
Our experiments show that an array of PMMA droplets aligned
along the substrate grooves form when LT−PMMA < LP,
irrespective of hE−PS. In case the PS layer is also thin, and the
as cast morphology of the film comprises of bilayer threads that
do not cover the entire width of the substrate groove, an array
of core − shell type droplets result. As the PS film becomes
thicker, the droplet formation is suppressed in favor of
undulating PS threads, which covers the submerged array of
PMMA droplets. For even thicker PS films, the top layer
remains intact, below which the PMMA droplet formation
takes place. Importantly, in all the cases, irrespective of the
thickness and nature (continuous/discontinuous) of the top PS
layer, the PMMA threads disintegrate due to Rayleigh
instability. We further show that if the bottom layer is
discontinuous but the threads covers the entire width of the
substrate groove (LT−PMMA = LP), then the PMMA threads do
not decay into isolated droplets due to lateral confinement with
in the substrate grooves and the final dewetted morphology
comprises of multi layer aligned undulating threads.
A variety of interesting structures also form when the bottom
layer is continuous. In majority of the cases, the dewetting
sequence proceeds with rupture of the bottom layer over the
substrate stripes (where the film is thinnest), followed by
rupture of the top PS layer at the same locations, resulting in
bilayer threads. However, we have also shown that in certain
specific cases, depending on the thickness of the two layers, the
two layers may dewet simultaneously resulting in the formation
of ordered and aligned structure of both the polymers
coexisting simultaneously. We also observe that a bottom
PMMA layer thicker than ∼100 nm remains stable and the top
PS film dewet over it or remain stable, depending on hE−PS.
A morphology phase diagram constructed based on our
experimental finding summarizes the different morphological
regimes. The phase diagram, along with plots that show the
variation of λA and λB with hE−PMMA and hT clearly reveal that
the periodicity of the dewetted bilayer features as well as the
periodicity of the bottom layer structures depend largely on the
thickness of the bottom layer and not on the overall bilayer
thickness. Further, the phase diagram revels that though the
overall morphology of the dewetted bilayer depends on the
thickness of both the layers, the morphology of the dewetted
bottom layer depends only on the thickness of the bottom layer
and is completely independent of the top layer thickness. We
further feel that if the geometry of the substrate remains
unaltered with change in its dimension, the morphological
types will most likely remain the same, with mere change in the
critical thickness at which transitions occur from one zone to
the other. A detailed investigation in this regard may be taken
up separately.
In summary, a comprehensive experimental study on
instability and dewetting in a thin polymer bilayer on a
topographically patterned substrates has been presented for the
947
Article
first time in this article, which points to many interesting
conditions of dissipative structure formation. Such structures
might find application in various areas such as microfluidics,
multilayer coating, organic electronics, etc. Further, dewetting
of a thin bilayer on a topographically patterned substrate might
eventually become a viable nonlithographic alternative for
creation of meso scale polymer patterns. We also feel that the
study will be helpful in interpretation and understanding of self-
organization processes occurring at the meso scale. This work
reports dewetting on a grating substrate of specific dimension
only, and we feel similar studies on substrates with more
complex pattern may lead to more exciting morphologies and
ordering and therefore should be taken up in future.
■
ASSOCIATED CONTENT
*
S Supporting Information
Approximate methodology and sample calculation for deter-
mining hL. This material is available free of charge via the
Internet at http://pubs.acs.org.
■
AUTHOR INFORMATION
Corresponding Author
*Telephone: +91−3222 283912. E-mail: rabibrata@che.iitkgp.
ernet.in.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
R.M. acknowledges the support of the Department of Science
& Technology (DST), Govt. of India, for funding the research
under its Nano Mission Program (SR/NM/NS-63/2010).
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