Langmuir 2007, 23, 7293-7298 7293

Transparent Superhydrophobic Films Based on Silica Nanoparticles

Javier Bravo,† Lei Zhai,‡ Zhizhong Wu,‡ Robert E. Cohen,*,§ and Michael F. Rubner*,‡
UniVersity of NaVarra, Spain, and Departments of Chemical Engineering and Materials Science and
Engineering, Massachusetts Institute of Technology, 77 Massachusetts AVenue,
Cambridge, Massachusetts 02139

ReceiVed January 18, 2007. In Final Form: April 16, 2007

We demonstrate a layer-by-layer processing scheme that can be utilized to create transparent superhydrophobic
films from SiO2 nanoparticles of various sizes. By controlling the placement and level of aggregation of differently
sized nanoparticles within the resultant multilayer thin film, it is possible to optimize the level of surface roughness
to achieve superhydrophobic behavior with limited light scattering. Transparent superhydrophobic films were created
by the sequential adsorption of silica nanoparticles and poly(allylamine hydrochloride). The final assembly was
rendered superhydrophobic with silane treatment. Optical transmission levels above 90% throughout most of the
visible region of the spectrum were realized in optimized coatings. Advancing water droplet contact angles as high
as 160° with low contact angle hysteresis (<10°) were obtained for the optimized multilayer thin films. Because of
the low refractive index of the resultant porous multilayer films, they also exhibited antireflection properties.

Introduction galvanic corrosion techniques,12 hydrothermal synthesis,18 radio

The appropriate texturing/roughening of surfaces on the nano-
and microscale is known to impart unusual wetting characteristics
that can span the range from superhydrophilic to superhydro-
phobic.1-10 The well-known lotus plant, long admired for its
unique self-cleaning properties, often serves as a natural model
for the design of synthetic superhydrophobic films. The surface
structure of this plant has two levels of roughness (on the micro-
and nanoscales) that enable the trapping of air under water
droplets, thereby contributing to the rolling water droplet effect
that is characteristic of a well-designed superhydrophobic
surface.11-13 Many different techniques have been used to obtain
surfaces with these unusual characteristics, including sol-gel
techniques,14-16 the sublimation of aluminum acetylacetonate,7,17
* To whom correspondance may be addressed. E-mail: recohen@mit.edu,
rubner@mit.edu.
† University of Navarra.
‡ Department of Materials Science and Engineering, MIT.
§ Department of Chemical Engineering, MIT.
(1) Cebeci, F. Ç.; Wu, Z.; Zhai, L.; Cohen, R. E.; Rubner, M. F. Langmuir
2006, 22, 2856.
(2) Zhai, L.; Berg, M. C.; Cebeci, F. Ç.; Kim, Y.; Milwid, J. M.; Rubner, M.
F.; Cohen, R. E. Nano Lett. 2006, 6, 1213.
(3) Wang, R.; Hashimoto, K.; Fujishima, A.; Chikuni, M.; Kojima, E.; Kitamura,
A.; Shimohigoshi, M.; Watanabe, T. Nature 1997, 388, 431.
(4) Miyauchi, M.; Nakajima, A.; Hashimoto, K.; Watanabe, T. AdV. Mater.
2000, 12, 1923.
(5) Bico, J.; Marzolin, C.; Quéré, D. Europhys. Lett. 1999, 47, 220.
(6) Shi, F.; Chen, X.; Wang, L.; Niu, J.; Yu, J.; Wang, Z.; Zhang, X. Chem.
Mater. 2005, 17, 6177.
(7) Nakajima, A.; Hashimoto, K.; Watanabe, T.; Takai, K.; Yamauchi, G.;
Fujishima, A. Langmuir 2000, 16, 7044.
(8) Shang, H. M.; Wang, Y.; Limmer, S. J.; Chou, T. P.; Takahashi, K.; Cao,
G. Z. Thin Solid Films 2005, 472, 37.
(9) Tadanaga, K.; Morinaga, J.; Minami, T. J. Sol-Gel Sci. Technol. 2000, 19,
211.
(10) Soeno, T.; Inokuchi, K.; Shiratori, S. Appl. Surf. Sci. 2004, 237, 543.
(11) Patankar, N. A. Langmuir 2004, 20, 8209.
(12) Wu, X.; Shi, G. Nanotechnology 2005, 16, 2056.
(13) Cheg, Y. T. Appl. Phys. Lett. 2005, 86, 144101.
(14) Hikita, M.; Tanaka, K.; Nakamura, T.; Kajiyama, T.; Takahara, A.
Langmuir 2005, 21, 7299.
(15) Wu, Y. L.; Tan, G. H.; Zeng, X. T.; Li, T. H.; Chen, Z. J. Sol-Gel Sci.
Technol. 2006, 38, 85.
(16) Shang, H. M.; Wang, Y.; Takahashi, K.; Cao, G. Z. J. Mater. Sci. 2005,
40, 3587.
(17) Nakajima, A.; Fujishima, A.; Hashimoto, K.; and Watanabe, T. AdV.
Mater. 1999, 11, 1365.
frequency plasma-enhanced CVD,19 and physical vapor deposi-
tion.20 Some of these methods establish suitably textured surfaces
directly from hydrophobic materials15,21,22 whereas others first
create a textured surface that is subsequently coated with a
hydrophobic thin film.7,8,16,23 All of them ultimately combine
high surface roughness and low surface energy to achieve
superhydrophobicity. Chen et al.,24 however, reported super-
hydrophobic surfaces based on a relatively hydrophilic material,
PHBV (poly(hydroxybutyrate-co-valerate)), which exhibits a
contact angle of 75.9° when fabricated with a smooth surface.
Superhydrophobic films with contact angles up to 158° and a
sliding angle of 7° have been obtained by electrospinning of
PHBV.
As a result of micrometer-scale roughness, superhydrophobic
films usually scatter light strongly. Transparent superhydrophobic
films, however, would be very desirable for use in many
applications such as self-cleaning windows and car windshields.
Several authors have reported that it is possible to realize high
transparency combined with high water droplet advancing contact
angles,7,9,17,21,25,26 but only a few studies also report low contact
angle hysteresis or a low water droplet sliding angle.23,27-29 These
later characteristics are required if a surface is to exhibit true
self-cleaning properties. In this article, we report on the
development of transparent superhydrophobic films based on
SiO2 nanoparticles. To accomplish this combination of properties,
we have utilized the layer-by-layer assembly method to control
(18) Shi, F.; Chen, X.; Wang, L.; Niu, J.; Yu, J.; Wang, Z.; Zhang, X. Chem.
Mater. 2005, 17, 6177.
(19) Hozumi, A.; Takai, O. Thin Solid Films 1997, 303, 222.
(20) Tavana, H.; Amirfazli, A.; Neumann, A. W. Langmuir 2006, 22, 5556.
(21) Yabu, H.; Shimomura, M. Chem. Mater. 2005, 17, 5231.
(22) Yoshida, N.; Abe, Y.; Shigeta, H.; Takami, K.; Osaki, H.; Watanabe, T.;
Hashimoto, K.; Nakajima, A. J. Sol-Gel Sci. Technol. 2004, 31, 195.
(23) Nakajima, A.; Abe, K.; Hashimoto, K.; Watanabe, T. Thin Solid Films
2000, 376, 140.
(24) Zhu, M.; Zuo, W.; Yu, H.; Yang, W.; Chen, Y. J. Mater. Sci. 2006, 41
(12), 3793.
(25) Gu, G.; Dang, H.; Zhang, Z.; Wu, Z. Appl. Phys. A 2006, 83, 131.
(26) Hozumi, A.; Takai, O. Thin Solid Films 1998, 334, 54.
(27) Ogawa, K.; Soga, M.; Takada, Y.; Nakayama, I. Jpn. J. Appl. Phys. 1993,
32, L614.
(28) Duparré, A.; Flemming, M.; Steinert, J.; Reihs, K. Appl. Opt. 2002, 41,
3294.
(29) Tadanaga, K.; Kitamuro, K.; Matsuda, A.; Minami, T. J. Sol-Gel Sci.
Technol. 2003, 26, 705.

10.1021/la070159q CCC: $37.00 © 2007 American Chemical Society

Published on Web 05/25/2007
7294 Langmuir, Vol. 23, No. 13, 2007
Figure 1. Simplified schematic of the multilayer film showing the
three main assembly blocks.
the placement and level of aggregation of differently sized
nanoparticles within the resultant multilayer thin film. Shiratori
and co-workers have previously reported ultra-water-repellent
films created by the layer-by-layer assembly of polyelectrolytes
and SiO2 nanoparticles,10 but they did not report any data about
the light transmittance of their films. In our case, we have fully
exploited the advantages of layer-by-layer processing to optimize
the level of roughness needed to obtain superhydrophobicity and
a low contact angle hysteresis and at the same time minimize
light scattering. Besides high transmittance and superhydro-
phobicity, very low levels of reflectivity can be also achieved
at specified visible wavelengths.
Experimental Section
Materials. Poly(sodium 4-styrenesulfonate) (Mw ) 70 000) (SPS),
poly(allylamine hydrochloride) (Mw ) 70 000 g/mol) (PAH), Ludox
TM-40 colloidal silica 40 wt % (20 nm diameter silica particles),
Ludox SM-30 colloidal silica 30 wt % (7 nm diameter silica particles),
and trichloro(1H,1H,2H,2H-perfluorooctyl)silane (97%) were ob-
tained from Sigma-Aldrich. Silica microspheres, (5% aqueous
dispersion, 50 nm ((10 nm) diameter silica nanoparticles) were
obtained from Polysciences, Inc. A pH 9.0 colorless buffer (VWR
International) was used for all silica nanoparticle solutions. All of
the chemicals were used as received without further purification.
All aqueous solutions were prepared using Milli-Q (Millipore) water
with a resistivity of 18.2 MΩ·cm.
Preparation of Multilayers. The deposition process of the
materials consisted of immersing the substrates (either microscope
glass slides or silicon wafers) repetitively into different aqueous
solutions. Although these films were created using different solutions
for the three main parts of the film (adhesion, body, and top layers,
as shown in Figure 1), the procedure and timing for the deposition
of each bilayer remained constant during the entire process. First,
the substrate was dipped into the cationic solution for 15 min followed,
by one 2 min and two 1 min rinsing steps using Milli-Q water. Then,
the substrate was dipped into the anionic solution for 15 min, followed
by the same rinsing steps.
The multilayers were composed of three main blocks. First,
adhesion layers were used to enhance the binding of the polymer-
nanoparticle system to the substrate. Similar results were obtained
without adhesion layers, although their use helped to promote more
uniform multilayer growth. For this part, PAH was used to create
the cationic solution (10-2 M based on the repeat unit, pH 4.0), and
SPS was used to create the anionic solution (10-2 M based on the
repeat unit, pH 4.0). Five bilayers of this polyelectrolyte pair were
deposited to create the adhesion-promoting multilayer [PAH (4.0)/
SPS (4.0)]5. For the body layers, PAH (10-2 M, pH 7.5) was used
to create the cationic solution. For the anionic solution, two differently
sized silica nanoparticles (50 and 20 nm, 0.03 wt % each) were used.
The roughness of the polyelectrolyte-silica multilayer films was
increased by adding salt to the silica nanoparticle suspension.30
Specifically, NaCl (0.1 M) was added to the solution containing the
(30) Sennerfors, T.; Bogdanovic, G.; Tiberg, F. Langmuir 2002, 18, 6410.
BraVo et al.
mixture of 50/20 nm silica particles. A pH 9.0 buffer solution was
used to stabilize the pH of this solution. The following notation will
be used to represent these multilayers: [PAH (7.5)/(50 + 20 nm)
SiO2 (9.0)]x, where x is the number of body bilayers deposited.
Although the films obtained in this way were quite rough, in order
to enhance the two-scale roughness necessary for superhydrophobic
films11-13 three additional bilayers containing only 20 nm SiO2
particles were added on top of the [PAH (7.5)/(50 + 20 nm) SiO2
(9.0)]x multilayer system. These will be referred to as top layers. The
cationic solution used for the top layers was 10-2 M PAH (pH 7.5).
A DI water solution of 20 nm silica particles (0.03 wt %) was the
anionic solution. Because the top layers are created from only three
bilayers, no pH adjustment or stabilization with buffer solution was
necessary. Particles of 7 nm diameter were also used for these top
layers in other experiments, but the results were similar to those
obtained with the 20 nm particles so they will not be reported for
the sake of simplicity. In addition, in an alternative approach to
creating transparent superhydrophobic coatings, body layers were
created with a combination of 7 and 20 nm particles and were
decorated with a few top layers of 20 nm particles. (See Supporting
Information for details.)
Some films were calcinated at 550 °C for 4 h to remove the
organic part of the film and improve the mechanical properties.
Finally, trichloro(1H,1H,2H,2H-perfluorooctyl) silane was deposited
by chemical vapor deposition (CVD) to change the surface chemistry.
Substrates coated with the multilayer films were introduced into a
vacuum chamber, and the pressure inside was reduced so that the
fluorosilane compound could evaporate at room temperature. The
fluorosilane molecules reacted with the surface of the film for 1 h.
Characterization of the Multilayers. Film thickness and
refractive index values were obtained using a Gaertner 126B
ellipsometer using a He-Ne 633 nm wavelength laser at an angle
of incidence of 70°. Root-mean-square (rms) roughness values were
determined using an atomic force microscope (AFM, nanoscope
IIIa, Digital Instruments) at three different points for each film.
UV-vis spectroscopy measurements were made on a Cary SE
spectrophotometer. Contact angle measurements were carried out
using a VCA-Optima 2000 (AST Products, Inc) with DI water drops
of around 3 µL applied to three different points for each film.
Advancing contact angle measurements were performed by adding
liquid to the water droplets, and receding contact angle measurements
were made by removing liquid from the drops.
Results and Discussion
The two key elements needed to create transparent superhy-
drophobic films from layer-by-layer-assembled silica nano-
particles are (1) control over the z-direction placement of
nanoparticles of different sizes and (2) control over the level of
nanoparticle aggregation. The layer-by-layer assembly process
provides the ability to place nanoparticles of different sizes
throughout the multilayer film in a controlled manner whereas
control over the assembly conditions (nanoparticle concentration,
composition, and solution pH) makes it possible to control
nanoparticle aggregation. To approximate the two levels of
texturing needed to realize a lotus effect (micrometer-scale texture
decorated with nanoscale particles), multilayers containing a
mixture of nanoparticles (50 + 20 nm diameter particles) were
first assembled onto a surface previously coated with adhesion
layers, followed by the assembly of three additional layers of the
smaller nanoparticles (20 nm diameter). Multilayers containing
the mixed nanoparticle sizes provide the larger-scale texture (and
some nanoscale texture) whereas the smaller nanoparticles
decorating the surface further enhance the nanoscale texture
needed to prevent water from penetrating the microstructure.
Assembly conditions were optimized to produce a level of
nanoparticle aggregation sufficient to create the lotus effect but
with minimum scattering of visible light. Although there are a
number of different ways to accomplish this goal, this article
Transparent Superhydrophobic Films
Figure 2. Thickness of multilayer films with different numbers of
[PAH (7.5)/(50 + 20 nm) SiO2 (9.0)] bilayers. Solid squares are for
films with top layers ([PAH (7.5)/(20 nm) SiO2]3, and open squares
are for films without top layers.
Figure 3. Refractive index of multilayer films with different numbers
of [PAH (7.5)/(50 + 20 nm) SiO2 (9.0)]x bilayers, with and without
top-layers and also calcinated and non-calcinated.
will focus on a particular multilayer system: multilayers of [PAH
(7.5)/(50 + 20 nm) SiO2 (9.0)] overcoated with three layers of
[PAH (7.5)/(20 nm) SiO2 (9.0)]. An alternative approach in which
body layers were constructed with a combination of 7 and 20
nm particles and decorated with a few top layers of 20 nm particles
can be found in Supporting Information. Please see the
Experimental Section for a description of the nomenclature used
to define a bilayer. A simplified schematic illustration of the
resultant multilayer film is shown in Figure 1.
Figure 2 shows how the thickness of the mixed nanoparticle
multilayers varies as a function of the number of deposited bilayers
(obtained by ellipsometry). Linear growth (28.3 nm per bilayer)
is observed up to at least 40 bilayers, suggesting that a well-
behaved layer-by-layer assembly process is possible with a
solution containing a mixture of differently sized nanoparticles.
As expected, the addition of the final three bilayers of smaller
nanoparticles (20 nm) results in a modest increase in film thickness
(on average, about 14 nm per bilayer). Figure 3 shows how the
refractive index of this multilayer system varies with the number
of bilayers deposited for both as-prepared and calcinated films
(to be discussed). The refractive index is found to be essentially
independent of film thickness, covering a range of about 1.22
to 1.26. The low refractive index of this multilayer system (the
SiO2 nanoparticles have an index of about 1.46 at 500 nm31)
indicates that a porous network is created during the assembly
process.1,32
Langmuir, Vol. 23, No. 13, 2007 7295
Figure 4. AFM rms roughness of multilayer films with different
numbers of [PAH (7.5)/(50 +20 nm) SiO2 (9.0)]x bilayers. All values
were obtained from films with top layers.
Figure 5. Transmittance of multilayer films with 20 to 40 bilayers
of [PAH (7.5)/(50 + 20 nm) SiO2 (9.0)]x and top layers. The
transmittance of a plain glass slide (substrate for the films) is also
plotted.
AFM measurements (Figure 4) reveal that the rms roughness
of this multilayer increases in a linear fashion as the number of
bilayers increases. Recent theoretical studies of layer-by-layer-
assembled polyelectrolytes and nanoparticles predict such
behavior and suggest that increasing roughness with an increasing
number of bilayers may be the result of incomplete coverage of
the substrate by the initially deposited polymer/nanoparticle
layers.33
Figure 5 shows the transmittance of multilayers containing
from 20 to 40 bilayers of mixed nanoparticles ([PAH (7.5)/(50
+ 20 nm) SiO2 (9.0)]x) plus an additional three bilayers of the
smaller nanoparticles. In the range of 20 to 25 bilayers, the
multilayers are quite transparent, exhibiting transmittance levels
close to (or higher than) that of the uncoated glass substrate. For
example, a 20-bilayer film exhibits a maximum transmittance of
about 94.6% at 584 nm whereas the transmittance of a plain
glass slide at this wavelength is only about 91.6%. This
enhancement of light transmission is due to the antireflection
properties of the film (to be discussed). As more bilayers are
added to the multilayer, the level of transmittance systematically
decreases as a result of the increasing roughness of the film and
(31) Krogman, K. C.; Druffel, T.; Sunkara, M. K. Nanotechnology 2005, 16,
S338.
(32) Mendelsohn, J. D.; Barrett, C. J.; Chan, V. V.; Pal, A. J.; Mayers, A. M.;
Rubner, M. F. Langmuir 2000, 16, 5017.
(33) Jeon, J.; Panchagnula, V.; Pan, J.; Dobrynin, A. V. Langmuir 2006, 22,
4629.
7296 Langmuir, Vol. 23, No. 13, 2007 BraVo et al.

Table 1. Select Properties of the [PAH (7.5)/(50 + 20 nm) SiO2

(9.0)]20 Multilayer System
without top layers with top layers
as-assembled calcinated as-assembled calcinated
films films films films
thickness (nm) 569.4 561.3 591.4 587.6
refractive index 1.235 1.216 1.239 1.213
rms roughness (nm) 45.2 42.4 48.2 45.0
advancing CA ∼7 <5 <5 <5
(before silane treatment)
advancing CA 154 152 161 157
(after silane treatment)
receding CA 134 134 156 150
(after silane treatment)

system. Typical values of several important properties of this

system are shown in Table 1 for multilayer films with and without
small nanoparticle top layers and before and after calcination.
Figure 6. Advancing contact angle and contact angle hysteresis as A number of interesting effects are revealed by these data.
a function of film roughness (rms value in nm).
First, prior to semifluorosilane treatment, all of the films (with
the exception of the non-calcinated 20 bilayer film without the
its increasing propensity to scatter light. As will become apparent
added small nanoparticle top layers) exhibit superhydrophilic
shortly, there is a clear tradeoff between high light transmission
behavior (rapid drop spreading to produce a contact angle of less
and superhydrophobicity.
than 5°). We have recently reported1 that multilayer films
Pilotek and Schmidt divided the wettability of surfaces into
containing a critical number of silica nanoparticle bilayers
three different regions for increasing roughness: smooth surfaces
assembled under specific conditions exhibit superhydrophilic
(low roughness values), the Wenzel regime (higher roughness
wetting characteristics due to the nanoporous nature of the film.
values), and superhydrophobic surfaces (highest roughness
A similar mechanism is responsible for the extreme wetting
values).34 They showed that contact angle hysteresis is very low
behavior of the mixed nanoparticle multilayers. The low refractive
for smooth surfaces, increases for films in the Wenzel state, and
index (about 1.23) exhibited by all mixed nanoparticle multilayers
is very low again for superhydrophobic surfaces. Hysteresis
supports the conclusion that these are nanoporous thin films. Not
essentially goes to zero at high roughness values for an ideal
surprisingly, the superhydrophilic mixed nanoparticle multilayers
self-cleaning film.14 Advancing contact angles and contact angle also exhibit antifogging properties.1 Second, it is clear that, for
hysteresis as a function of film roughness for the multilayers
this multilayer system, the realization of low contact angle
films of this work are shown in Figure 6. The contact angles
hysteresis requires the presence of the three top layers containing
were measured on calcinated films containing three outermost
only the smaller nanoparticles. In all cases, the advancing contact
bilayers of the smaller nanoparticles. The surfaces of all films
angle of silane-treated films is greater than 150°; however, low
were rendered hydrophobic with a silane treatment (Experimental
contact angle hysteresis (5-7°) is obtained only with added layers
Section). As the number of mixed nanoparticle bilayers is
of smaller nanoparticles. Thus, an enhancement (aggregated
increased, both the advancing and receding contact angles
nanoparticles always exhibit some level of nanoscale texturing)
increase, approaching values of about 160°. In addition, as more
of the second level of nanotexturing that is now well recognized
bilayers are added to the multilayer film, the contact angle
as a key characteristic of the lotus leaf11-13 is needed to ensure
hysteresis initially decreases dramatically and then more slowly
that water droplets are not easily pinned (Wenzel state) but rather
as more bilayers are added. Thus, because the roughness of the
are free to roll with minimal tilting of the surface (Cassie state).
multilayer increases as the number of deposited bilayers increases,
Han and colleagues35 also found that ideal superhydrophobic
the film transitions from Wenzel state behavior to superhydro-
properties were realized only from ZrO2-based nanoparticle
phobic behavior. With 20 bilayers of the mixed nanoparticles
multilayers when they were further textured with 11 nm silica
(rms roughness ∼50 nm), the contact angle hysteresis is about
nanoparticles.
7° whereas for 40 bilayers (rms roughness ∼75 nm) it drops to
An AFM image of a [PAH (7.5)/(50 + 20 nm) SiO2 (9.0)]20
about 3°. Thus, multilayer films with 20 or more mixed bilayers
multilayer film is shown in Figure 7, which reveals the type of
exhibit superhydrophobic characteristics (contact angle greater
surface texturing/particle aggregation created by the assembly
than 150° and low contact angle hysteresis) with nearly ideal
of these mixed nanoparticle multilayers: submicrometer-sized
superhydrophobic properties being observed when 40 bilayers
aggregated nanoparticles with a raspberry-like nanometer-sized
are assembled.
outer surface. (Note that additional AFM images showing how
Optimized Superhydrophobic Multilayers. The results above the surface texture changes when 20 nm single-nanoparticle top
suggest that there is a limited window of opportunity (20-25 layers are added to 7/20 nm mixed particle layers can be found
mixed nanoparticle bilayers) for creating nanoparticle-based in Supporting Information. With this nanoparticle system, it is
superhydrophobic coatings with high levels of transparency. If easier to visualize the changes in texture introduced by the addition
more limited transparency is acceptable (50-80%), however, of the single-nanoparticle top layers.) This structure is reminiscent
coatings with excellent superhydrophobic properties can be easily of the SiO2 nanoparticle films obtained by Shiratori et al.10 and
realized (30-40 bilayers). The rest of this article will focus on Takahara et al.14 Both realized good superhydrophobic behavior;
the properties of the multilayer system that exhibits the highest however, only the latter film was reported to be transparent.
level of light transmission and acceptable superhydrophobic Reihs et al.28 obtained a very similar structure using ZrO2
properties, specifically, the [PAH (7.5)/(50 + 20 nm) SiO2 (9.0)]20
(35) Han, J. T.; Zheng, Y.; Cho, J. H.; Xu, X.; Cho, K. J. Phys. Chem. B 2005,
(34) Pilotek, S.; Schmidt, H. K. J. Sol-Gel Sci. Technol. 2003, 26, 789. 109, 20773.
Transparent Superhydrophobic Films Langmuir, Vol. 23, No. 13, 2007 7297

Figure 7. AFM image of as-prepared [PAH (7.5)/(50 + 20 nm) Figure 8. Typical transmittance and reflectance spectra of a [PAH
SiO2 (9.0)]20 + top layers. (7.5)/(50 + 20 nm) SiO2 (9.0)]20 + top-layers film compared to
those of a plain glass slide.
nanoparticles. The contact angle of these films was not very high
(143°), but the slide angle was lower than 10°. Reihs also reported
very low light scattering at 633 nm. It should be noted that
multilayer films assembled with body layers containing only 50
nm particles and 20 nm single-nanoparticle top layers exhibited
high contact angle hysteresis (157° advancing contact angle,
116° receding contact angle) demonstrating that, for the conditions
explored in this work, mixed nanoparticle body layers are needed
to achieve low contact angle hysteresis.
There are clearly many processing parameters that can be
adjusted to control the level of nanoparticle aggregation needed
to achieve transparent, superhydrophobic multilayer coatings
based on polymer/nanoparticle assemblies. For example, the
polydispersity of the nanoparticle sizes, the concentrations of
the nanoparticle and polymer solutions, and solution pH and
ionic strength are all important parameters to consider when Figure 9. Experimental and simulated reflectance of a [PAH (7.5)/
optimizing the micro- and nanoscale textures of the resultant (50 + 20 nm) SiO2 (9.0)]20 + top-layers film.
multilayer films. In this work, a combination of mixed nanoparticle
body layers and a few additional top layers assembled from
nanoparticles of a single size produces the desired effect. For the
processing conditions used in this work, the top layers are needed
to further enhance the nanoscale texture of the aggregated
nanoparticles within the film, which in turn lowers the contact
angle hysteresis.
Calcination is used to improve mechanical robustness and
film adhesion to glass. The calcination process produces a small
decrease in the thickness, refractive index, and roughness of the
multilayer film (Table 1). It also slightly lowers the advancing
contact angle and slightly increases the contact angle hysteresis, Figure 10. Image of a glass slide coated with a transparent,
possibly because of the slightly lower roughness. Calcination superhydrophobic multilayer with antireflection properties: [PAH
has a major impact on the adhesion and mechanical robustness (7.5)/(50 + 20 nm) SiO2 (9.0)]20 + top-layers film. The right side
of the glass slide is coated with the multilayers.
of the multilayer. Whereas as-prepared films could be removed
from the substrate by rubbing with an alcohol-soaked wipe,
calcinated films remained intact after this rubbing procedure. result of the specific optical thickness of this film. Figure 9
Detailed studies of the changes in mechanical properties brought shows the reflectance spectrum predicted theoretically36 for the
about by calcination are currently underway. same optimized transparent superhydrophobic film. The data
utilized for creating this simulated spectrum (thickness ) 587.6
The low refractive index of the [PAH (7.5)/(50 + 20 nm) SiO2 nm and refractive index ) 1.213) were obtained from ellipsometry
(9.0)]20 multilayer films also gives rise to antireflection properties1 measurements of multilayer films on silicon wafers. Good
as presented in Figure 8. Compared to an uncoated glass slide, agreement is observed between the predicted and experimentally
a multilayer-coated glass slide exhibits significantly reduced observed reflectance spectra. The small differences in the values
reflective losses throughout the visible region. The minimum of the reflectance at peak maxima and minima may be due to
reflectance value for a coated slide is about 0.22% at 562 nm, the nanocorrugated structure of the film that gives rise to a more
and the maximum reflectance value is about 5.2% (710 nm). In complicated refractive index profile than the assumed single-
contrast, the reflectance of the plain slide is close to 8% throughout
the entire visible region of the spectrum. The minima and maxima (36) Zhai, L.; Nolte, A. J.; Cohen, R. E.; Rubner, M. F. Macromolecules 2004,
observed in the reflectance spectrum of the coated slide are the 37, 6113.
7298 Langmuir, Vol. 23, No. 13, 2007
value index profile. Figure 10 shows an optical image of an
optimized multilayer film that is superhydrophobic, transparent,
and antireflective.
Conclusions
We demonstrate a layer-by-layer processing scheme that can
be utilized to create transparent superhydrophobic films from
SiO2 nanoparticles of various sizes. By controlling the placement
and level of aggregation of differently sized nanoparticles within
the resultant multilayer thin film, it is possible to optimize the
level of surface roughness to achieve superhydrophobic behavior
with limited light scattering. The nanoporous nature of the
multilayer film also gives rise to antireflection properties.
Acknowledgment. This work was supported in part by the
MRSEC Program of the National Science Foundation under award
BraVo et al.
DMR 02-13282 and the DARPA BOSS program. This work also
made use of equipment at the MIT Institute for Soldier
Nanotechnologies and the shared experimental facilities at the
MIT Center for Materials Science and Engineering. J.B. was
supported by the Spanish Ministry of Science and Education
(TEC2006-12160/MIC) and Gobierno de Navarra research grants.
We thank Dr. Xiaoxia Sheng, Mr. Adam Nolte, Mrs. Jenny
Lichter, Mr. Daeyeon Lee, Dr. Zhi Li, Mr. Erik Williamson, and
Mr. Zekeriyya Gemici for assistance with this work.
Supporting Information Available: AFM images showing
how surface texture changes when 20 nm single nanoparticle top layers
are added to 7/20 nm mixed particle layers with corresponding contact
angle information. This material is available free of charge via the Internet
at http://pubs.acs.org.
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