9620 Langmuir 2000, 16, 9620-9626

Wetting Behavior of Block Copolymers on Self-Assembled

Films of Alkylchlorosiloxanes: Effect of Grafting Density

Richard D. Peters, Xiao M. Yang, Tae K. Kim, and Paul F. Nealey*

Department of Chemical Engineering and Center for Nanotechnology, University of Wisconsin,
Madison, WI 53706

Received June 14, 2000. In Final Form: September 5, 2000

The wetting behavior of thin films of symmetric poly(styrene-b-methyl methacrylate) was investigated
on self-assembled (SA) films of octadecyltrichlorosilane on Si/SiOx with varying grafting density. The
different types of SA organic films were produced by changing the deposition times (t) in solution. Two
types of wetting behavior were observed on partial self-assembled monolayers (SAMs); 8 Å < thickness
< 23 Å): (1) for short deposition times with t ) 1-10 h, asymmetric wetting with the poly(methyl
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methacrylate) block wetting the substrate, and (2) for t ) 12 h, neutral wetting with lamellae oriented
perpendicular to the substrate. For t ) 21-24 h, the polymer films dewet complete SAMs (thickness )
26 Å (the theoretical thickness for a complete SAM)). A metastable morphology of symmetric wetting with
the polystyrene block wetting the substrate was observed on SA films with long deposition times, greater
than 30 h (28 Å < thickness < 36 Å). The different wetting behavior of the block copolymer films on the
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different types of SA films was determined to depend on the chemistry and structure of the surface. These
results have important implications regarding the use of SAMs of alkylsiloxanes to control the wetting
behavior of block copolymers for patterning applications.

Introduction surfaces exhibited dewetting and symmetric, neutral, and

The wetting behavior of polymers on self-assembled
monolayers (SAMs) is of technological interest for a
number of micro- and nanofabrication strategies involving
the self-assembly of block copolymers and polymer blends.
Surfaces are typically patterned with SAMs of different
chemical functionality, and transfer of the pattern into a
polymer layer occurs by controlled wetting. In this paper,
we demonstrate that the structure of SAMs of alkylsi-
loxanes on Si/SiOx, in addition to chemical functionality,
plays an important role in determining the wetting
behavior of polymer films. Understanding these effects is
critical for exploiting SAMs of alkylsiloxanes for applica-
tions involving controlled wetting of surfaces.
The wetting behavior of block copolymer films has been
shown previously to depend on the chemistry of the
substrate.1,2 To tune the wetting behavior of block
copolymers of poly(styrene-b-methyl methacrylate) (P(S-
b-MMA)) to achieve symmetric, neutral, and asymmetric
wetting, Mansky et al. used random copolymer brushes
of poly(styrene-r-methyl methacrylate), with varying
chemical compositions that were grafted to the substrate.3
We have previously investigated the use of SAMs of
alkylsiloxanes on Si/SiOx to regulate the wetting behavior
of thin films of diblock copolymers.4 The surface chemistry
of the SAMs was modified by exposure to X-rays in air to
incorporate oxygen into polar functional groups on the
surface of the SAMs.5 Thin films of P(S-b-MMA) on these
* To whom correspondence should be addressed. E-mail: nealey@
engr.wisc.edu.
(1) Russell, T. P.; Coulon, G.; Deline, V. R.; Miller, D. C. Macromol-
ecules 1989, 22, 4600.
(2) Coulon, G.; Russell, T. P.; Deline, V. R.; Green, P. F. Macromol-
ecules 1989, 22, 2581.
(3) Mansky, P.; Russell, T. P.; Hawker, C. J.; Pitsikalis, M.; Mays,
J. Macromolecules 1997, 30, 6810.
(4) Peters, R. D.; Yang, X. M.; Kim, T. K.; Sohn, B. H.; Nealey, P. F.
Langmuir 2000, 16, 4625.
(5) Kim, T. K.; Yang, X. M.; Peters, R. D.; Sohn, B. H.; Nealey, P. F.
J. Phys. Chem. B 2000, 104, 7403.
asymmetric wetting with increasing exposure dose. The
interfacial energies between the two blocks of the copoly-
mer and the SAM-covered surfaces were estimated using
the Fowkes-van Oss-Chaudhury-Good (FOCG) model
of surface tension, and the wetting behavior was directly
correlated to the interfacial energy. This system was used
to create chemically nanopatterned surfaces to guide the
orientation and macroscopic order of the self-assembled
structure in thin films of P(S-b-MMA).6,7
A number of groups have used SAMs of alkanethiols on
gold to control polymer wetting. Genzer et al.8 investigated
the wetting of binary polymer blends on mixed SAMs of
CH3- and COOH-terminated alkanethiols on gold and
observed a wetting reversal transition as the composition
of the SAM changed. Nisato et al.9 and Karim et al.10
patterned striped SAMs of CH3- and COOH-terminated
alkanethiols on gold, and Boltau et al.11 patterned stripes
of gold and SAMs of CH3-terminated alkanethiols on gold
to direct the phase separation of polymer blends on the
patterned surfaces. In these experiments, the wetting
behavior of polymer was controlled by the functionality,
or surface chemistry, of the SAMs. Heier et al. used striped
SAMs of CH3- and HO-terminated alkanethiols on gold
and demonstrated that the surface pattern could be
transferred to films of poly(styrene-b-2-vinylpyridine)
(P(S-b-2VP)).12-15 The pattern of the copolymer film
(6) Yang, X. M.; Peters, R. D.; Nealey, P. F. Macromolecules, submitted
for publication, 2000.
(7) Peters, R. D.; Yang, X. M.; Wang, Q.; de Pablo, J. J.; Nealey, P.
F. J. Vac. Sci. Technol. B, in press.
(8) Genzer, J.; Kramer, E. J. Phys. Rev. Lett. 1997, 78, 4946.
(9) Nisato, G.; Ermi, B.; Douglas, J. F.; Karim, A. Macromolecules
1999, 32, 2356.
(10) Karim, A.; Douglas, J. F.; Lee, B. P.; Glotzer, S. C.; Rogers, J.
A.; Jackman, R. J.; Amis, E. J.; Whitesides, G. M. Phys. Rev. E 1998,
57, R6273.
(11) Boltau, M.; Walheim, S.; Mlynek, J.; Krausch, G.; Steiner, U.
Nature 1998, 391, 877.
(12) Heier, J.; Kramer, E. J.; Walheim, S.; Krausch, G. Macromol-
ecules 1997, 30, 6610.

10.1021/la000822+ CCC: $19.00 © 2000 American Chemical Society

Published on Web 10/21/2000
Wetting Behavior of Block Copolymers
consisted of different surface topography over adjacent
regions of the patterned SAM. On top of the CH3-
terminated SAMs, the lamellae were oriented primarily
perpendicular to the substrate, indicative of a neutral
substrate with respect to the diblock copolymer. This
neutral wetting behavior was different than the expected
parallel orientation of lamellae with the polystyrene (PS)
block wetting the substrate. Heier et al. concluded that
the neutral wetting was due to the structure of the CH3-
terminated SAMs and that defects in the monolayer film
allowed the poly(2-vinylpyridine) (PVP) block to interact
with the Au layer.13
Disadvantages of using SAMs of alkanethiols on Au for
patterning applications include thermal instability and
incompatibility with silicon processing. Thermal instabil-
ity may be problematic because the polymer systems must
often be annealed at high temperatures to increase
mobility and induce self-assembly. Delamarche et al.16
reported that SAMs of alkanethiols on Au had limited
thermal stability at 100 °C. During annealing of block
copolymer films, however, Heier et al.13 reported that
desorption of alkanethiols on Au at high temperatures
occurs after the establishment of well-ordered structures.
SAMs of alkylsiloxanes on Si/SiOx have two major
advantages over SAMs of alkanethiols on Au: (1) they
are thermally stable under vacuum up to temperatures
of 740 K17 and are thermally stable when annealed under
a polymeric confining layer,18 and (2) they are compatible
with standard silicon processing in the microelectronics
industry. The disadvantage of using SAMs of alkylsilox-
anes compared to alkanethiols on Au is the difficulty in
reproducibly depositing the organic films.19-22 Small
changes in humidity and temperature, for example, can
result in deposition of films with completely different
structures.
The general objective of this paper was to quantify the
difference in wetting behavior of block copolymers on self-
assembled (SA) films of alkylsiloxanes with varying
grafting density (structure). A specific objective related
to patterning applications was to identify deposition
conditions of SA films of alkylsiloxanes that result in the
desired wetting behavior of a block copolymer film. For
patterning applications using SAMs of octadecyltrichlo-
rosilane (OTS) exposed to X-rays and P(S-b-MMA), for
example, the desired wetting behavior is preferential
wetting of the PS block on unexposed regions of SAMs of
OTS and preferential wetting of the poly(methyl meth-
acrylate) (PMMA) block on exposed regions of SAMs of
OTS. In this paper, we demonstrate that the PMMA block
preferentially wets the substrate on partial SAMs with
thicknesses < 17 Å (deposition time (t) < 12 h), neutral
wetting with perpendicular lamellae occurs on partial
(13) Heier, J.; Genzer, J.; Kramer, E. J.; Bates, F. S.; Walheim, S.;
Krausch, G. J. Chem. Phys. 1999, 111, 11101.
(14) Heier, J.; Sivaniah, E.; Kramer, E. J. Macromolecules 1999, 32,
9007.
(15) Heier, J.; Kramer, E. J.; Groenewold, J.; Fredrickson, G. H.
Macromolecules 2000, 33, 6060.
(16) Delamarche, E.; Michel, B.; Kang, H.; Gerber, C. Langmuir 1994,
10, 4103.
(17) Kluth, G. J.; Sung, M. M.; Maboudian, R. Langmuir 1997, 13,
3775.
(18) Calistri-Yeh, M.; Kramer, E. J.; Sharma, R.; Zhao, W.; Rafailov-
ich, M. H.; Sokolov, J.; Brock, J. D. Langmuir 1996, 12, 2747.
(19) Silberzan, P.; Leger, L.; Aussere, D.; Benattar, J. J. Langmuir
1991, 7, 1647.
(20) Brzoska, J. B.; Shahidzadeh, N.; Rondelez, F. Nature 1992, 360,
719.
(21) Brzoska, J. B.; Ben Azouz, I.; Rondelez, F. Langmuir 1994, 10,
4367.
(22) Parikh, A. N.; Allara, D. L.; Ben Azouz, I.; Rondelez, F. J. Phys.
Chem. 1994, 98, 7577.
Langmuir, Vol. 16, No. 24, 2000 9621
SAMs with thickness ) 17.4 Å (t ) 12 h), dewetting occurs
on complete SAMs with thickness ) 26 Å (t ) 21-24 h),
and the PS block preferentially wets the substrate for
SAMs with thicknesses > 26 Å (t > 30 h) for annealing
times of ∼ 24 h.
Experimental Section
Materials. Polished test-grade silicon 〈100〉 wafers were
purchased from Tygh Silicon. Octadecyltrichlorosilane (CH3-
(CH2)17SiCl3, 95%) was purchased from Gelest and was used as
received. Symmetric P(S-b-MMA) was purchased from Polymer
Source, Inc. The number average molar mass was 51,200 g/mol,
the polydispersity was 1.06, the styrene volume fraction was
0.48, and the bulk lamellar period (Lo) was 30 nm. Toluene (99.8%,
anhydrous), chloroform (99+%, anhydrous), and poly(acrylic acid)
(25 wt % solution in water) were purchased from Aldrich and
were used without further purification. Ethanol (dehydrated,
200 proof) was purchased from Aaper Alcohol and Chemical Co.
and was used as received. Ruthenium tetroxide (0.5% aqueous
solution) was purchased from Polysciences, Inc.
Deposition of Self-Assembled Organic Films. Silicon
wafers were cleaved into pieces approximately 2 cm × 2 cm and
were cleaned by immersion in a piranha solution (7/3 (v/v) of
98% H2SO4/30% H2O2; Caution! Piranha solution reacts violently
with organic compounds and should not be stored in closed
containers) at 90 °C for 30 min. The silicon pieces were
immediately rinsed with deionized water (resistivity g 18 MΩ/
cm) several times and were blown dry with nitrogen. The cleansed
substrates were immersed in a 0.25% (v/v) solution of OTS in
toluene in a glovebox with a nitrogen atmosphere. The substrates
were removed from the OTS solutions after deposition times
between 1 and 48 h. After the substrates were removed from the
silane solution, they were rinsed with chloroform for ap-
proximately 30 s, and excess chloroform was allowed to evaporate.
The SA organic films (CH3(CH2)17SiO/SiOx) were baked at 120
°C for 5 min, then were removed from the glovebox. The SA films
were rinsed with absolute ethanol and were dried under a stream
of nitrogen.
Measurement of Contact Angles. Advancing and receding
contact angles of deionized water were measured on the SA films
at ambient temperature using a Ramé-Hart model 100 goni-
ometer. Contact angles were measured on the opposite edges of
at least three drops and averaged. The values were reproducible
to within 1.3°.
Ellipsometry Measurements. Ellipsometry measurements
were made on a Rudolf Research/Auto EL II ellipsometer using
a He-Ne Laser (λ ) 632.8 nm) at an incident angle of 70° relative
to the surface normal of the substrates. The thicknesses of the
SA films and the oxide layer cannot be measured simultaneously,
and at least three separate spots were measured on each substrate
before and after deposition of the SA film to determine the
thickness of the oxide layer and the thickness of the SA film plus
the oxide layer. The thickness of the oxide layer of silicon wafers
was typically 12-18 Å. A refractive index of 1.45 was used for
calculation of the thicknesses of the SA films and the oxide.
Sample Preparation. Thin films of P(S-b-MMA) were
deposited onto clean or SA film-covered Si/SiOx substrates by
spin coating (2500 rpm) from a dilute solution (2% w/w) of the
copolymer in toluene. The initial thicknesses of the films were
determined by scraping some of the polymer away from the
surface with a razor blade and by measuring the difference in
height between the substrate and the surface of the film using
an Alpha Step 200 profilometer (0.5-nm resolution). The polymer
films were annealed at 180 °C in a vacuum oven for 24 h. After
annealing, the morphology of the films was investigated using
optical microscopy, atomic force microscopy (AFM), and trans-
mission electron microscopy (TEM).
Optical Microscopy. Polymer films were imaged using an
Olympus model BX600 optical microscope in reflection mode.
Island and hole topography resulted in contrast (different
interference colors) due to differences in film thickness.
Atomic Force Microscopy. The surface topography of the
polymer films was imaged using a Nanoscope III MultiMode
atomic force microscope from Digital Instruments in contact
9622 Langmuir, Vol. 16, No. 24, 2000
Table 1. Advancing and Receding Contact Angles of
Deionized Water and Thicknesses of SA Films of OTS
with Different Deposition Times
deposition advancing contact receding contact thickness
time (hrs) angle of water (deg) angle of water (deg) (Å)
1 70 ( 2 53 ( 2 8.7
4 65 ( 2 45 ( 2 12.5
6 89 ( 2 64 ( 2 18
12 89 ( 2 62 ( 2 17.4
18 93 ( 2 65 ( 2 22.7
21 105 ( 2 80 ( 2 27.5
24 103 ( 2 86 ( 2 25.6
30 105 ( 2 82 ( 2 28.9
48 110 ( 2 85 ( 2 36
mode. A triangular cantilever with an integral pyramidal Si3N4
tip was used. The typical imaging force was on the order of 10-9
N.
Transmission Electron Microscopy. The internal structure
of the polymer films was studied using TEM. TEM was performed
on a JEOL 200CX at 200 kV in the bright field mode at the
Materials Science Center at the University of Wisconsin. Samples
were imaged in plan-view. Samples were prepared for TEM
analysis as described by Fasolka et al.23 A layer of carbon (ca.
20-nm thick) was evaporated onto the surface of films and then
covered with a 25% aqueous solution of poly(acrylic acid) (PAA).
After drying the sample in air overnight, the P(S-b-MMA)-carbon-
PAA composite was peeled off the substrate and floated on
deionized water with the PAA side down. After the PAA layer
dissolved, the floating film was collected onto TEM grids. The
films were then exposed to the vapor of the RuO4 solution for 15
min. The RuO4 selectively stains the PS block and provides
contrast in electron density.
Results and Discussion
Characterization of SA Films of OTS for Different
Deposition Times. The advancing and receding contact
angles of deionized water and the thicknesses of the SA
films of OTS are shown in Table 1 as a function of
deposition time. A bare Si/SiOx substrate was completely
wet by water, and contact angles were too low to measure.
After an hour of deposition, both the advancing and
receding contact angles increased significantly, and a
partial layer of OTS, 8.7 Å in thickness, was measured
using ellipsometry. The advancing and receding contact
angles and the thickness increased with increasing
deposition times. For deposition times between 21 and 30
h, the advancing and receding contact angles plateaued
near 104° and 83°, respectively, and the thickness
plateaued near 27.3 ( 1.6 Å. After 48 h of deposition, the
contact angles changed only slightly, but the thickness of
the OTS layer grew to 36 Å.
We have categorized our SA films into three regimes:
complete SAMs, partial SAMs, and “thick” SAMs. Com-
plete SAMs have been reported to be highly ordered, quasi-
crystalline films in which the hydrocarbon chains are
oriented nearly perpendicular to the surface.22,24,25 The
SA films described in Table 1 with deposition times
between 21 and 24 h are considered to be complete SAMs
based on the agreement between our thickness measure-
ments and the reported thickness of 26 Å for SAMs of
OTS,26 and this categorization refers primarily to the
density of the films. The contact angles of these films were
slightly lower than the reported value of 110°,26 and the
(23) Fasolka, M. J.; Harris, D. J.; Mayes, A. M.; Yoon, M.; Mochrie,
S. G. J. Phys. Rev. Lett. 1997, 79, 3018.
(24) Tillman, N.; Ulman, A.; Schildkraut, J. S.; Penner, T. L. J. Am.
Chem. Soc. 1988, 110, 6136.
(25) Maoz, R.; Sagiv, J. J. Colloid Interface Sci. 1984, 100, 465.
(26) Wasserman, S. R.; Tao, Y. T.; Whitesides, G. M. Langmuir 1989,
5, 1074.
Peters et al.
lower values are probably due to decreased in-plane order
of the alkylsiloxane film compared to other OTS films
reported in the literature.22,26,27 This decrease in in-plane
order is likely due to the deposition conditions used with
extremely low levels of water as discussed below. We define
partial SAMs as those films with density less than
complete SAMs. Decreased density results in more
disorder and increased defect density than in complete
SAMs. Organic films with deposition times less than 21
h are considered to be partial SAMs. Thick SAMs are films
with thicknesses typically 1.1-1.4 times the thickness of
a complete SAM. The molecular configuration of the excess
alkylsilane ligands is unclear, but the excess material
cannot be removed by washing with solvent or wiping
with a cotton swab. The films with deposition times greater
than 30 h are considered to be thick SAMs.
The formation and structure of self-assembled mono-
layers of alkylsiloxanes, specifically SAMs of OTS, have
been studied extensively on various substrates and under
different deposition conditions.22,27-34 Two mechanisms
of growth are supported in the literature. In the mech-
anism known as the “uniform” model, silane molecules
are distributed homogeneously over the substrate in a
disordered, liquidlike manner.33,34 With increasing cover-
age, the disordered film is transformed into a densely
packed, quasi-crystalline structure. In the mechanism
known as the “island” model, domains of well-ordered,
fully extended OTS molecules are heterogeneously grown
on the substrate, and these domains are separated by
uncovered regions of the substrate.27,30,31 These islands
typically have dimensions on the order of hundreds of
nanometers.30,31 With increasing deposition time, more
domains are adsorbed until complete coverage of the
substrate is achieved. Brunner et al.29 and Vallant et al.28
found that the dominant mechanism of growth of SAMs
of OTS is determined by two major factors: (1) concentra-
tion of OH groups on the surface of the substrate and (2)
concentration of water in the silane solutions.
The concentration of OH groups on the surface affects
the mobility of the adsorbed OTS molecules.29 The OH
groups act as nucleation and bonding sites for the
formation of the monolayers. On mica substrates with
very few OH groups, the OTS molecules are very mobile
and can aggregate easily into ordered domains or “islands”
before bonding to the substrate. On silicon substrates with
many silanol groups, the OTS molecules have limited
mobility and bond more quickly to the substrate. On these
substrates, the OTS molecules adsorb more uniformly over
the surface of the substrate and, initially, in a more
disordered configuration.
The presence of water in the OTS solutions causes the
OTS molecules to oligomerize in solution. These oligomers
have been shown to adsorb to surfaces more quickly than
single molecules,31 and the adsorption of these oligomers
gives rise to the formation of well-ordered “islands” on
surfaces in fractal patterns.31 With increasing deposition
(27) Tidswell, I. M.; Rabedeau, T. A.; Pershan, P. S.; Kosowsky, S.
D.; Folkers, J. P.; Whitesides, G. M. J. Chem. Phys. 1991, 95, 2854.
(28) Vallant, T.; Brunner, H.; Mayer, U.; Hoffmann, H.; Leitner, T.;
Resch, R.; Friedbacher, G. J. Phys. Chem. B 1998, 102, 7190.
(29) Brunner, H.; Vallant, T.; Mayer, U.; Hoffmann, H.; Basnar, B.;
Vallant, M.; Friedbacher, G. Langmuir 1999, 15, 1899.
(30) Bierbaum, K.; Grunze, M.; Baski, A. A.; Chi, L. F.; Schrepp, W.;
Fuchs, H. Langmuir 1995, 11, 2143.
(31) Schwartz, D. K.; Steinberg, S.; Israelachvili, J.; Zasadzinski, J.
A. N. Phys. Rev. Lett. 1992, 69, 3354.
(32) Allara, D. L.; Parikh, A. N.; Rondelez, F. Langmuir 1995, 11,
2357.
(33) Wasserman, S. R.; Whitesides, G. M.; Tidswell, I. M.; Ocko, B.
M.; Pershan, P. S.; Axe, J. D. J. Am. Chem. Soc. 1989, 111, 5852.
(34) Banga, R.; Yarwood, J.; Morgan, A. M. Langmuir 1995, 11, 618.
Wetting Behavior of Block Copolymers Langmuir, Vol. 16, No. 24, 2000 9623

Figure 1. AFM images of thin films of symmetric P(S-b-MMA) on a Si/SiOx substrate (a) and SA films of OTS with deposition
times of (b) 4 h, hole formation characteristic of asymmetric wetting on a partial SAM; (c) 12 h, featureless surface characteristic
of neutral wetting on a partial SAM; and (d) 48 h, island formation characteristic of symmetric wetting on a thick SAM. In parts
a, b, and d, the step heights of the terraces equal approximately 30 nm (Lo) in each case.

time, the gaps between islands are filled by other adsorbed
islands and single molecules. Vallant et al. have shown
that with decreasing concentrations of water, the growth
of islands decreases and the formation of monolayers
becomes more uniform.28 In addition, Angst et al. showed
that films of OTS on nonhydrated SiO2 were less ordered
than films of OTS deposited on well-hydrated SiO2 and
that both contact angles of water and thicknesses of
the monolayers were lower on the nonhydrated sur-
faces.35
We have examined the surface topography of SA films
of OTS using AFM. In all cases, we have found uniform
coverage of OTS molecules on the surface with root-mean-
square (rms) roughness less than 1 nm. Our experimental
method of depositing monolayers in a N2 atmosphere in
a glovebox (dew point less than -60 °C (10 ppm)) on
(35) Angst, D. L.; Simmons, G. W. Langmuir 1991, 7, 2236.
piranha-cleaned silicon wafers follows conditions that
would favor the “uniform” model of growth that produces
more disordered SA films.
Wetting Behavior of P(S-b-MMA) on SA Organic
Films. Thin films of symmetric P(S-b-MMA) were de-
posited on the SA films of OTS described in Table 1. All
of the films had an initial thickness of 67 ( 2 nm (2.2Lo).
SA films with different times of deposition produced
different wetting behavior in the thin films of diblock
copolymers after annealing. The formation of topography
on the surface of the films and the type of topography
were used to determine the wetting of the block copolymer
at the substrate. For example, consider the film of P(S-
b-MMA) deposited on Si/SiOx that is shown in part a of
Figure 1. It is well-known that the PMMA block wets SiOx
and that the PS block is segregated to the free interface
leading to asymmetric wetting conditions. For the film
9624 Langmuir, Vol. 16, No. 24, 2000
thickness of 2.2Lo, holes form for asymmetric wetting and
islands form for symmetric wetting. From part a of Figure
1, holes were observed to form in the film deposited on
SiOx, indicating asymmetric wetting with the PMMA block
wetting the substrate and the PS block wetting the free
interface.
AFM images of annealed films of P(S-b-MMA) on SA
films of OTS with deposition times between 4 and 48 h are
shown in parts b-d of Figure 1. Hole formation was
observed in polymer films supported on partial SAMs with
deposition times less than 12 h (part b of Figure 1). Hole
formation indicated asymmetric wetting with the PMMA
block at the substrate. This behavior is surprising in light
of the structure of the partial SAMs. We observed uniform
growth of these partial SAMs with no discernible domains
of OTS and rms roughness < 1 nm. Only methyl and
methylene groups should be presented at the surface. In
the absence of polar interactions, dispersive forces are
the only contributions to the interfacial energy between
the polymer and the surface. If the surface is composed
only of CH2 and CH3 groups, then the PS block should
have a lower interfacial energy than the PMMA block on
the partial SAMs because PS has a lower total surface
tension than PMMA. However, for deposition times less
than 12 h, the PMMA block wet the substrate. Miller et
al.36 have shown that long-range van der Waals forces can
act over distances larger than the thickness of SAMs of
alkanethiols on gold to affect the wetting behavior of a
liquid on the SAM-covered surface. These forces do not
act over distances as large as 1 nm in our system because
the substrate (Si/SiOx) is an insulator with a much lower
dielectric constant than gold. In fact, for partial SAMs of
OTS on Si/SiOx substrates, the van der Waals forces
between Si/SiOx and the polymer film are negligible for
separation distances greater than 5 Å when the gap is
filled with a hydrocarbon. Therefore, for the PMMA block
to wet substrates covered with partial SAMs, the PMMA
chains must penetrate the alkylsiloxane layer to allow for
short-range interactions between PMMA segments and
SiOH groups or adsorbed water in the siloxane network.
Even though the SAMs used in this study are believed to
uniformly cover the substrates, the lateral density of the
partial SAMs must be less than that of a complete SAM,
and the PMMA blocks must be able to penetrate into the
defects of the partial SAM.
For a specific partial SAM with a deposition time of 12
h, the thin film (part c of Figure 1) was featureless on the
free surface, which is characteristic of neutral wetting at
the substrate with perpendicular orientation of the
lamellae at the substrate. AFM measurements verified
the smoothness of the surface of the annealed film (rms
roughness < 2 nm). A plan-view TEM image of the film
from part c of Figure 1 is shown in Figure 2. The contrast
between the PS and PMMA domains was achieved by
staining the PS domains with RuO4. The laterally
alternating domains of PS and PMMA confirm a perpen-
dicular orientation of the lamellae in the film. After 12 h
of deposition, the concentration of OTS molecules on the
surface increased such that the penetration of PMMA
blocks into the partial monolayer likely decreased. The
short-range interactions between PMMA and the sub-
strate were balanced with the interfacial interactions
between PS and the methyl and methylene groups on the
surface of the partial SAM. This surface was neutral in
interfacial energy with respect to both blocks of the
copolymer.
(36) Miller, W. J.; Abbott, N. L. Langmuir 1997, 13, 7106.
Peters et al.
Figure 2. Plan-view TEM image of thin film of P(S-b-MMA)
on a partial SAM of OTS with a deposition time of 12 h. Dark
regions correspond to PS due to staining with RuO4. The
alternating light and dark regions confirm an orientation of
the lamellae perpendicular to the substrate and the neutral
wetting behavior of the polymer film.
It is unclear whether the lamellae were oriented
perpendicular to the substrate throughout the thickness
of the film or whether a mixed morphology occurred with
perpendicular lamellae near the substrate and parallel
lamellae near the free surface. Neutral surfaces have been
shown to induce a perpendicular orientation of micro-
domains in thin films of block copolymers.3,4,37,38 For films
with thicknesses greater than 3.0Lo, the lamellae formed
a mixed morphology,3,38 except when the annealing
temperature was raised such that the surface tensions of
the two blocks were equal and perpendicular lamellae
extended throughout the thickness of the film.37 On neutral
surfaces under similar annealing conditions as employed
for this paper, perpendicular lamellae were observed on
the free surface of a 2.2Lo thick film (same thickness as
used in this paper) using lateral force microscopy.4
Whether the perpendicular orientation of the lamellae
extended throughout the film thickness was inconse-
quential for this paper, and we did not pursue this issue
further.
For complete SAMs of OTS, either we were unable to
spin-coat thin films of P(S-b-MMA) or the films completely
dewet from the substrate during annealing. For complete
SAMs, the interactions between the polymer and the
surface diminished as more OTS molecules chemisorbed
onto the surface to complete the monolayer. Only CH3
groups are presented at the surface of complete SAMs of
OTS, and the surface tension (γOTS) is approximately 23
mJ/m2.4 Nonpolar PS is more likely to wet complete SAMs
of OTS than polar PMMA. The spreading coefficient for
PS (S ) γOTS - γPS - γPS/OTS) was calculated from the
surface tension of PS (γPS ) 35.8 mJ/m2) and the interfacial
energy between PS and the surface (γPS/OTS ) 1.2 mJ/m2).4
The negative spreading coefficient predicted nonwetting
conditions for P(S-b-MMA) on complete SAMs of OTS.
For thick SAMs, island formation was observed on the
free surface of the films (part d of Figure 1). Island
formation was characteristic of symmetric wetting for the
initial film thickness with the PS block wetting both the
substrate and free interface. Partial dewetting of the films,
however, was observed after annealing at 180 °C for
several days (Figure 3). Thermodynamics dictates that
the films dewet (S < 0), but the dewetting process is
kinetically hindered. Island formation indicative of sym-
metric wetting is a metastable morphology. The config-
uration of the excess alkylsilane ligands on the surface of
thick SAMs is unclear, but this material probably grows
in a disordered manner, lending itself to more chain-
(37) Mansky, P.; Russell, T. P.; Hawker, C. J.; Mays, J.; Cook, D. C.;
Satija, S. K. Phys. Rev. Lett. 1997, 79, 237.
(38) Huang, E.; Russell, T. P.; Harrison, C.; Chaikin, P. M.; Register,
R. A.; Hawker, C. J.; Mays, J. Macromolecules 1998, 31, 7641.
Wetting Behavior of Block Copolymers
Figure 3. Optical micrograph of film of P(S-b-MMA) on a thick
SAM annealed at 180 °C for several days. The film exhibited
island formation (dark areas) and partial dewetting.
chain contacts and interdigitation between the excess
material and the polymer than with complete SAMs. These
interactions decrease the mobility of the polymer in contact
with the SA film, as compared to the mobility on complete
SAMs of OTS.
The wetting behavior of thin films of block copolymers
has been determined to depend on the interfacial energy
between the surfaces and each block of the copolymer.4,39
In a previous paper, interfacial energies were calculated
from contact angle data of three test liquids using the
FOCG model of surface tension.40 We attempted to use
this approach to analyze the wetting behavior of P(S-b-
MMA) on partial and thick SAMs of OTS, but the results
were unsatisfactory. Estimation of surface and interfacial
energies using the FOCG model depends on contact angle
measurements that require homogeneous surfaces. The
FOCG model, therefore, is applicable when probing surface
chemistry effects but not surface structural effects. The
wetting of P(S-b-MMA) on partial and thick SAMs depends
on both surface chemistry and structure. The wetting
behavior of films of block copolymers on SAMs can be
considered a sensitive characterization tool for probing
the structure of SAMs. Sharp transitions in wetting
behavior were observed on different SAMs that exhibited
only small changes in both contact angle and thickness.
The wetting behavior of the block copolymers amplifies
small differences in the SAM structure that cannot be
detected by contact angle and thickness measurements.
As mentioned in the Introduction, Heier et al. observed
neutral wetting behavior of P(S-b-2VP) films on CH3-
terminated SAMs of alkanethiols on Au after annealing
at 176 °C.12-15 The wetting behavior was consistent with
penetration of the PVP block into defects in the SAM
structure and interaction of the PVP block with the
underlying gold. They concluded that the defects in the
SAMs were present in the initial monolayer structure and
were not introduced during the annealing process. The
conclusions were based on concentration versus depth
profiles of sulfur in the samples obtained using dynamic
secondary ion mass spectroscopy (dSIMS).13 Significant
differences in the concentration of sulfur at the polymer/
substrate interface were not observed for annealing times
up to 4 h. Based on the results presented in this paper and
information in the literature, we believe that defects in
the SAMs of alkanethiols on Au were not present after
stamping but were related to thermal desorption during
annealing. Several groups have shown that stamped SAMs
of alkanethiols (contact times greater than 0.3 s) are
extremely well-ordered, with few defects, and exhibit
(39) Mansky, P.; Liu, Y.; Huang, E.; Russell, T. P.; Hawker, C. Science
1997, 275, 1458.
(40) van Oss, C. J.; Chaudhury, M. K.; Good, R. J. Chem. Rev. 1988,
88, 927.
Langmuir, Vol. 16, No. 24, 2000 9625
similar properties as SAMs deposited from solution.41,42
It is also well-known that SAMs of alkanethiols on Au are
more ordered than SAMs of alkylsiloxanes on Si/SiOx. We
observed dewetting of P(S-b-MMA) block copolymers on
CH3-terminated complete SAMs of alkylsiloxanes and did
not observe neutral wetting behavior on partial SAMs
unless the imperfections in the SAMs were extensive. The
thickness of the partial SAMs that exhibited neutral
wetting was ∼9 Å less than the thickness of the complete
SAMs (26 Å), and the difference in contact angle between
the partial and complete SAMs was ∼15°. It is possible
that the results obtained with dSIMS by Heier et al. were
misleading in that the data provided no information
concerning the integrity of the SAM. Sulfur may remain
at the interface between the polymer and the substrate
(within the depth resolution of the experiment) for long
periods of time but may not remain physisorbed to the
gold.
We are interested in the wetting behavior of block
copolymer films on SA films of alkylsiloxanes because we
are developing a technique to macroscopically orient block
copolymer domains on chemically patterned surfaces
where we use SA films of alkylsiloxanes as imaging layers
to produce the chemically patterned surface.6,7,43,44 A key
aspect of this technique is that the adjacent regions of the
chemically patterned surface are preferentially wet by
the different blocks of the copolymer. We have shown
previously that SA films of alkylsiloxanes can be chemi-
cally modified by exposure to X-rays in air and that the
wetting behavior of diblock copolymers on these surfaces
can be controlled.4,5 As shown in our previous work,
however, films of P(S-b-MMA) dewet from complete SAMs
of OTS.4 Such dewetting is undesirable for this application.
In this paper, we show that thick SAMs of OTS are
preferentially wet by the PS block without dewetting
within annealing times of interest (24 h). Therefore, when
thick SAMs of OTS are patterned using X-ray lithography,
the desired wetting behavior is achieved with the PS block
preferentially wetting unexposed regions and the PMMA
block preferentially wetting exposed regions of the SA
film.
Conclusions
Partial, complete, and thick SAMs of OTS were produced
by varying the deposition time of the SA films. Thin films
of P(S-b-MMA) exhibited asymmetric wetting on partial
SAMs with deposition times less than 12 h, indicating
penetration of the PMMA blocks into defects of the SA
film. Neutral wetting was observed on partial SAMs with
a deposition time of 12 h, and dewetting was observed on
complete SAMs. Symmetric wetting on thick SAMs was
a metastable morphology due to kinetically hindered
dewetting due to interdigitation of the polymer with excess
material on the SA film. The wetting behavior of the
polymer films depended on both chemical and structural
properties of the SA films. The use of SA films of OTS as
imaging layers to create chemically patterned surfaces to
direct pattern formation in P(S-b-MMA) films requires
the use of thick SAMs that are preferentially wet by the
PS block and that are kinetically hindered to dewet.
(41) Larsen, N. B.; Biebuyck, H.; Delamarche, E.; Michel, B. J. Am.
Chem. Soc. 1997, 119, 3017.
(42) Eberhardt, A. S.; Nyquist, R. M.; Parikh, A. N.; Zawodzinski, T.;
Swanson, B. I. Langmuir 1999, 15, 1595.
(43) Yang, X. M.; Peters, R. D.; Kim, T. K.; Nealey, P. F. J. Vac. Sci.
Technol., B 1999, 17, 3203.
(44) Yang, X. M.; Peters, R. D.; Kim, T. K.; Nealey, P. F.; Brandow,
S. L.; Chen, M.-S.; Shirey, L. M.; Dressick, W. J. Langmuir, submitted
for publication, 2000.
9626 Langmuir, Vol. 16, No. 24, 2000 Peters et al.

Acknowledgment. Funding for this work was pro-
vided by the Semiconductor Research Corporation (Grant
Number 98-LP-452), an NSF Small Grant for Explora-
tory Research (Grant Number CTS-9708944), and an
NSF Career Award (Grant Number CTS-9703207). Fa-
cilities were supported by DARPA/ONR (Grant Number
N00014-97-1-0460) and the NSF (Grant Number DMR-
95-31009).
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