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org/Langmuir
© 2009 American Chemical Society

Covalent Layer-by-Layer Assembled Superhydrophobic

Organic-Inorganic Hybrid Films
Sonia Amigoni, Elisabeth Taffin de Givenchy, Mickael Dufay, and Fr
ed
eric Guittard*
Universit

e de Nice-Sophia Antipolis, Laboratoire de Chimie des Mat

eriaux Organiques et M

etalliques
(CMOM), Equipe Chimie Organique aux Interfaces, Parc Valrose, 06108 Nice Cedex 2, France

Received April 19, 2009. Revised Manuscript Received May 28, 2009

Using the concept of covalent layer-by-layer assembly (covalent LbL), used until now for the elaboration of films
from polymers or dendrimers, we have constructed hybrid organic/inorganic surfaces by alternating different layers
of amino-functionalized silica nanoparticles (295 nm diameter) and epoxy-functionalized smaller silica nanoparticles
(20 nm diameter). The so-realized macromolecular edifice leads to a hierarchical integration of nanoscale textures. Then
hydrophobization of the last layer of amino-functionalized silica particles was carried out by grafting a new designed
highly fluorinated aldehyde, creating a monomolecular layer via the formation of an imine function. Five highly
fluorinated surfaces were built, and their water-repellent abilities were directly correlated to the surface topologies (i.e.,
the number of layers of silica nanoparticles and their organization on the glass support). The hydrophobicity increased
with the number of layers and stable highly water-repellent surfaces (static contact angle with water of 150 ( 3° and a
contact angle hysteresis of 12°) were obtained with the alternation of nine layers. This result demonstrates the possibility
to construct covalent LbL edifices with functionalized silica nanoparticles of different sizes and open this field for the
elaboration of responsive, sensing, and therapeutic surfaces with improved film stability.

Introduction microparticulate assembled structures on solid substrate.12-16

Controlling and modifying the surface roughness of materials
is one of the most studied prospects of the past decade.1 Indeed,
the appropriate texturing/roughening of surfaces in the nano- and
microscale is known to impart unusual optical, wetting, and
mechanical characteristics and, in particular, can amplify hydro-
phobicity which plays an increasing role in numerous industrial
applications. Two factors have to be controlled in order to
produce highly hydrophobic surfaces: their topography and their
chemical composition.2-7 Regularly structured surfaces provide
useful models for quantitatively evaluating relationship between
wettability and surface structure, whereas for practical applica-
tions, irregularly structured surfaces provide the advantage of
simplicity. Among all the procedures known in the literature
(lithographic patterning,8 plasma or laser etching,9 acidic corro-
sion,10 sol-gel synthesis, etc.),11 the layer-by-layer thin film
technique (LbL) is a method of choice to realize nano- or
Indeed, the successive deposition of silica particles of different
sizes via the LbL process lead easily to the building of rough
surfaces17,18 and has been widely used to enhance the hydro-
phobic properties of low surface energy material such as fluori-
nated coatings.19-25 However, the conventional use of highly
charged materials to build the LbL assemblies by means of
electrostatic interactions presents some key limitations as a
possible disassembly with changes of pH or ionic strength.26
In this paper we report the synthesis of original designed
surfaces that explores the recent concept of covalent layer-by-
layer assembly.27 This process, already applied to polymer or
dendrimer LbL assemblies,28 allows the construction of films with
high stability. Unlike the majority of LbL reports that use
preformed polymers to “stick” the layers together (charged
polymers17,29 or other more sophisticated ionic systems30), our
concept is based on the successive covalent grafting of func-
tionalized silica nanoparticules onto a previously silanized glass

*To whom correspondence should be addressed: Tel þ33 (0)4 92 07 61 59,
fax þ33 (0)4 92 07 6156, e-mail Frederic.Guittard@unice.fr.
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(2) Darmanin, T.; Guittard, F. J. Am. Chem. Soc. 2009, in press (DOI: 10.1021/
ja901392s).
(3) Darmanin, T.; Guittard, F. Langmuir 2009, 25, 5463.
(4) Campbell, J. L.; Breedon, M.; Latham, K.; Kalantar-zadeh, K. Langmuir
2008, 24, 5091.
(5) Zheng, Y.; Wynne, K. J. Langmuir 2007, 23, 11964.
(6) Sun, C.; Zhao, X.-W.; Han, Y.-H.; Gu, Z.-Z. Thin Solid Films 2008, 516,
4059.
(7) J€arn, M.; Brieler, F. J.; Kuemmel, M.; Grosso, D.; Lind
en, M. Chem. Mater.
2008, 20, 1476.
(8) Oner, D.; McCarthy, T. J. Langmuir 2000, 16, 7777.
(9) Baldacchini, T.; Carey, J. E.; Zhou, M.; Mazur, E. Langmuir 2006, 22, 4917.
(10) Taffin de Givenchy, E.; Amigoni, S.; Martin, C.; Andrada, G.; Caillier, L.;
G
eribaldi, S.; Guittard, F. Langmuir 2009, 25, 6448.
(11) Zhang, G.; Wang, D.; Gu, Z. Z.; M€ohwald, H. Langmuir 2005, 21, 9143.
(12) Pavan, K. A.; Jian, L. Surf. Coat. Technol. 2008, 202, 2690.
(13) Crespo-Biel, O.; Dordi, B.; Maury, P.; Reinhoudt, D. N.; Huskens, J.
Chem. Mater. 2006, 18, 2545.
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(15) Clark, S. L.; Hammond, P. T. Adv. Mater. 1998, 10, 1515.
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(17) Bravo, J.; Zhai, L.; Wu, Z.; Cohen, R. E.; Rubner, M. F. Langmuir 2007, 23,
7293.
(18) Soeno, T.; Inokuchi, K.; Shiratori, S. Appl. Surf. Sci. 2004, 237, 543.
(19) Gu, G.; Dang, H.; Zhang, Z.; Wu, Z. Appl. Phys. A: Mater. Sci. Process.
2006, 83, 131.
(20) Tsai, P.-S.; Yang, Y.-M.; Lee, Y.-L. Langmuir 2006, 22, 5660.
(21) Su, C.; Li, J.; Geng, H.; Wang, Q.; Chen, Q. Appl. Surf. Sci. 2006, 253, 2633.
(22) Ji, J.; Fu, J.; Shen, J. Adv. Mater. 2006, 18, 1441.
(23) Soeno, T.; Inokuchi, K.; Shiratori, S. Trans. Mater. Res. Soc. Jpn. 2003, 28,
1207.
(24) Jisr, R. M.; Rmaile, H. H.; Schlenoff, J. B. Angew. Chem., Int. Ed. 2005, 44,
782.
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Am. Chem. Soc. 2004, 126, 3064.
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Chem. Soc. Rev. 2007, 36, 707.
(27) Bergbreiter, D. E.; Liao, K.-S. Soft Matter 2009, 5, 23.
(28) Liu, Y. L.; Bruening, M. L.; Bergbreiter, D. E.; Crooks, R. M. Angew.
Chem., Int. Ed. Engl. 1997, 36, 2114.
(29) Yancey, S. E.; Zhong, W.; Heflin, J. R.; Ritter, A. L. J. Appl. Phys. 2006, 99,
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Langmuir 2009, 25(18), 11073–11077 Published on Web 07/14/2009 DOI: 10.1021/la901369f 11073
Article
Scheme 1. Construction of the Covalent LbL Building (i) Amine-Functionalized Particles (AP), EtOH, Sonication; (ii) Epoxy-Functionalized
Particles (EP), EtOH, Sonication; (iii) the Same as (i); and (iv) 2-Perfluorohexylethyl-4-formylthiobenzoate (Aldehyde F), Na2SO4, EtOH
support to lead to a highly stable hybrid organic/inorganic film
(as illustrated in Scheme 1).
The covalent connection of the silica particles is constituted
by a hydrocarbon flexible linker authorizing their self-assembly
to form a nanorough surface. Then, as superhydrophobicity
depends not only on the topology but also on the surface
chemistry, a monomolecular layer of highly fluorinated molecules
is directly grafted on the last layer of the hybrid edifice. The
wettability, the surface properties, and the morphologies of the
resulting hybrid materials are also reported and discussed.
Experimental Methods
Materials. 3-Glycidoxypropyltrimethoxysilane (GPS), (3-ami-
nopropyl)trimethoxysilane (AMS), fumed silica (14 nm), tetraethyl
orthosilicate (TEOS), ammonium hydroxide (30% in water),
4-carboxybenzaldehyde, dicyclocarbodiimide (DCC), and all other
chemicals were obtained from Aldrich. Glass wafers used were
microscope slides (25 mm  75 mm) cut into 12.5 mm  25 mm
pieces.
Procedures. 1. Silanization of Glass Surfaces. Glass
slides were washed with a 50/50 solution of HCl (36 wt %) in
methanol for 40 min followed by thorough rinsing in methanol
and dried. The slides were then activated in H2SO4 (97 wt %) for
20 min and rinsed with water. GPS (0.8 mL) or AMS (0.8 mL) and
3 drops of acetic acid were added in 8 mL of ethanol. The solution
was stirred at room temperature for 30 min. A glass slide
previously washed was then dipped into this solution and finally
cured at 120 °C for 3 h. The sample was washed three times with
ethanol to eliminate excess of silane.
2. Epoxy Silica Particles (20 nm) (EP). Fumed silica (2 g),
GPS (7 mL), and anhydrous toluene (75 mL) were charged in a
250 mL round-bottom flask equipped with a mechanical stirrer.
The mixture was heated at 126 °C for 3 h under N2. The reac-
tion was followed by cooling at room temperature. The particles
11074 DOI: 10.1021/la901369f
Amigoni et al.
were washed three times for 1 h with anhydrous toluene before
centrifugation (1600 rpm). Finally, the substrate was dried at
53 °C for 12 h and at 100 °C for 2 h. The resulting particles have
diameters of 20 ( 2 nm with a polydispersity of 0.05. Elementary
analysis of the purified silica particles afforded: C: 17.4%, H:
3.0%, which corresponds to ∼2.4 mequiv/g of epoxy groups.
3. Amine Silica Particles (∼295 nm) (AP). TEOS (13.2 mL),
deionized water (1.08 mL), and ethanol (5.24 mL) were mixed
with an ammonium hydroxide solution (30% in water, 3.56 mL),
heated at 50 °C for 8 h, and then cooled at room temperature to
afford colloidal silica. This colloidal silica and the appropriate
amount of AMS (molar ratio of TEOS/AMS=10/1) were heated
at 70 °C for 6 h. The final solution was ultrasonicated for 30 min.
The suspension was used readily after for the grafting onto glass
support. The particles have a diameter of about 295 nm with a
polydispersity of 0.8. Elementary analysis of the purified silica
particles afforded: C: 12.1%, H: 3.2%, N: 3.6%, which corre-
sponds to ∼2.5 mequiv/g of amine functions.
4. Covalent Layer-by-Layer Assemblies (Surfaces 1 to 5).
Glass slides silanized with GPS were ultrasonicated in an AP
solution (2 wt % in 8 mL of ethanol) for 3 h at room temperature.
The glass slides were then washed with ethanol before drying at
120 °C for 1 h to afford surface 1. The reaction could then be
repeated with EP (1 wt % of epoxy silica particles in 8 mL of
ethanol) to afford surface 10 . Several cycles could be repeated to
afford surfaces 2 to n.
5. Synthesis of 2-Perfluorohexylethyl-4-formylthiobenzoate
(Aldehyde F). Methylene chloride (20 mL), 4-carboxyben-
zaldehyde (2 g, 13.3 mmol), and DCC (13.3 mmol) were stirred
at room temperature for 1 h. 2-Perfluorohexylethanethiol
(13.3 mmol) was then added dropwise. After 24 h the bulk
was filtered and the solvent evaporated under vacuum. The
crude product was purified by column chromatography with
methylene chloride as eluent. 5.23 g (77% yield) of 2-perfluor-
ohexylethyl-4-formylthiobenzoate was obtained as a white solid.
1
H NMR (CDCl3/TMS δ ppm J Hz): 10.11 (1H, CHO, s);
Langmuir 2009, 25(18), 11073–11077
Amigoni et al.
8.11 (2HAr, d, JHH =8.2 Hz); 7.98 (2HAr, d, JHH =8.2 Hz); 3.33
(2H, COSCH2, t, JHH =8.0 Hz); 2.51 (2H, CH2C6F13, tt, JHF =
18.0 Hz, JHH =8.0 Hz). 19F NMR (CDCl3, δ ppm): -81.25; -
114.93; -122.35; -123.32; -123.80; -126.59. IR: 1658 cm-1,
1702 cm-1. Mp=70 °C.
6. Imine Formation (Surfaces 0F to 5F). Glass slides sila-
nized with AMS and glass surfaces 1 to 5 were immersed into
absolute ethanol (8 mL) with small amounts of Na2SO4. Aldehyde
F (10 wt % in ethanol, 5 mL) was added to the solution. The
mixture was stirred for 3 h. The modified glass slides were finally
washed with absolute ethanol and dried at 100 °C for 1 h to afford
highly fluorinated surfaces 0F to 5F.
Characterization. 1. Molecular Structure. NMR ex-
periments were carried out using a Br€ uker AC 200 MHz spectro-
meter. The spectra were recorded using deuterated solvents. The
mass spectra were carried out using a Thermo Finnigan spectro-
meter and electronic ionization at a 70 eV by direct introduc-
tion. IR spectra were performed with a Perkin-Elmer Paragon
1000 FI-IP spectrometer. Elemental analysis was performed using
a Thermo Electron Eager 300 elemental analyzer.
2. Nanoparticle Sizes (AP and EP). The average particle
size, size distributions, and surface charges were determined by
Zeta Sizer (Malvern Instruments, Model 3000 HSA, France).
3. Contact Angles and Surface Energy Determination.
Static contact angles, dynamic contact angles measurements,
and the deducted surface free energy of polymer samples were
performed using the sessile drop method on a motorized syringe
mechanism equipped Kr€ uss DSA 10 contact angles goniometer
interfaced to image-capture software. They were recorded at 25 (
1 °C. Measurements of static contact angle were made with
deionized water, diiodomethane, and hexadecane taking an aver-
age of five 1 μL drops with each type of reference liquid.
Reproducibility was within 3°. Dynamic contact angles were
performed with a motorized syringe at velocities of the three-
phase contact line in the range from 0.1 to 1.5 mm min-1. The
advancing and receding contact angles for water were evaluated
by axisymmetric drop shape analysis profile.31
4. Surface Roughness. A VEECO noncontacting laser pro-
filometer (WYKO NT1100) was used to assess the three-dimen-
sional surface roughness of the ground surfaces at nanometer
resolution in terms of arithmetic mean roughness (Ra).
Scanning electron microscopy (SEM) observations were car-
ried out with a JEOL 6700F microscope.
Results and Discussion
Construction of LbL Films. Silica nanoparticles with differ-
ent sizes and different surface functionalities are consecutively
grafted in a covalent manner onto glass supports previously
chemically modified by silanization with GPS. The nanoparticles
utilized are two sized functionalized silica nanoparticles: epoxy-
functionalized particles (EP) are 20 nm diameter commercially
available nanoparticles silanized with glycidoxypropyltrimethox-
ysilane, and amine-functionalized particles (AP) are 295 nm
diameter prepared nanoparticles, silanized with (3-aminopropyl)-
trimethoxysilane. As illustrated in Scheme 1, the first layer
of silica nanoparticles (surface 1) is achieved by dipping the
silanized glass substrate in a colloidal suspension of 295 nm
diameter amine-functionalized silica (AP), previously prepared
according to the Str€ober process32 and silanized with AMS,
to afford reactive NH2 groups at the surface of the nanopar-
ticles. The amine functions can then react with 20 nm diameter
epoxy-functionalized silica (EP) by ring-opening of the epoxy
groups induced by a nucleophilic attack to afford surface 10 .
To successively bind the layers together, we were inspired by Ming
(31) Hoorfar, M.; Neumann, A. W. J. Adhes. 2004, 80, 727.
(32) St€ober, W.; Fink, A.; Bohn, E. J. Colloid Interface Sci. 1968, 26, 62.
Langmuir 2009, 25(18), 11073–11077
Article
Scheme 2. Chemical Reactions Involved in the Fluorination of the
LbL Last Layer
and co-workers’ work33 where raspberry-like particles are fabri-
cated by covalently bond epoxy- and amine-based silica particles.
The reaction of the latest layer composed of EP allows adding a
second stratum of AP (surface 2). This cycle of reactions can be
repeated as many times as the number of layers is needed. N cycles
lead to n different surfaces: surface 3 corresponds to 3 layers of AP
(surface 4: 4 layers; surface 5: 5 layers of AP; ...). The covalent
LbL buildings with controlled number of layers are, in all cases,
ended by silica amino particles AP that can easily react with a lot
of other molecules.
Surface 5 is used to investigate the stability of the edifices. The
film was immersed in different aqueous media for 4 h: 0.9%
normal saline or buffered solutions at pH 4.5, 7, and 8.5. Laser
profilometry of the surface after immersion shows no difference
from that of the freshly prepared one. The films were also found to
be stable in a range of organic solvents (ethanol, acetone, ethyl
acetate, and cyclohexane).
Surface Chemical Hydrophobization. The formation of an
imine function by the reaction with an aldehyde moieties with the
AP layer seemed to us a rapid and efficient way (Scheme 1) to
introduce the hydrophobic moiety. So, we have designed a highly
fluorinated aldehyde (coded aldehyde F) able to quantitatively
react with the amino groups of the surface (Scheme 2). In this
aldehyde, the perfluorinated tail is associated with a phenyl unit to
achieve a stable low energy surface. Indeed, in a previous study
devoted to the creation of nonreconstructing water-repellent
surfaces, we have demonstrated that the rigidity induced by the
introduction of a mesogenic core (phenyl unit in this case)
associated with the “fluorophobic effect”34 of a perfluorinated
tail is able to stimulate the auto-organization of the monolayer35
and then could contribute to reach high water contact angles along
with weak value of hysteresis. The structure of the fluorinated
agent chosen for this study is derived from the monomers skeleton,
previously described in the literature,36-38 comprising one phenyl
unit as the mesogenic core linked to a fluorinated tail via
a thioester spacer. The synthesis of aldehyde F is realized by
reacting perfluorohexylethanethiol and 4-carboxybenzaldehyde
(33) Ming, W.; Wu, D.; van Benthem, R.; de With, G. Nano Lett. 2005, 5, 2298.
(34) Wang, J.; Mao, G.; Ober, C. K.; Kramer, E. J. Macromolecules 1997, 30,
1906.
(35) Cailler, L.; Taffin de Givenchy, E.; Geribaldi, S.; Guittard, F. J. Mater.
Chem. 2008, 18, 5382.
(36) Taffin de Givenchy, E.; Guittard, F.; Bracon, F.; Cambon, A. Liq. Cryst.
1999, 26, 1163.
(37) Taffin de Givenchy, E.; Guittard, F.; Bracon, F.; Cambon, A. Liq. Cryst.
1999, 26, 1371.
(38) Fornasieri, G.; Guittard, F.; Geribaldi, S. Liq. Cryst. 2003, 30, 251.
DOI: 10.1021/la901369f 11075
Article Amigoni et al.

Figure 1. SEM images of (a) one layer of AP particles: surface 1; (b) two layers of AP (and one layer of EP): surface 2; (c, d) five layers of AP
(and four layers of EP): surface 5. The insets represent contact angle with water of the surface once reacted with the fluorinated molecules
(surfaces 1F (a), 2F (b), and 5F (d), respectively). Scale bar corresponds to 10 μm for (a), (b) and (c) and to 1 μm for (d).

Figure 2. Morphology of surfaces 1 and 5 obtained from laser noncontacting profilometer.

using DCC as coupling agent. Its reaction with the LbL assem-
blies, via the formation an imine linker, leads to surfaces 1F to 5F.
A reference surface (surface 0F) is also prepared from a glass wafer
silanized with AMS and functionalized with the aldehyde F
(Scheme 1).
Topology. SEM is used to examine the effect of the number of
layers increment on the film morphologies. Figure 1 shows SEM
analysis of surfaces 1, 2, and 5, indicating different degrees of
surface roughness and porosity of the samples. It reveals that
morphology of the edifice changes considerably all along the layer
additions. For surface 1 (Figure 1a), the particles do not homo-
geneously cover the surface, and some lines are designed on the
support during the first deposition of the AP layer. The distribu-
tion is then more covering for surface 2 (Figure 1b).
Figure 1c,d shows the erratic particle distribution in sur-
face 5, leading to a (pseudo-) random surface. This “natural”
tendency to aggregate into porous structure gives quite dif-
ferent textures than those attained from on-demand topogra-
phies obtained with Langmuir-Blodgett depositions,20,39 but
as shown by the insets in Figure 1, the so-created highly rough
surface 5F is able to reach superhydrophobic properties as the
water partially sit on the air pockets trapped between the voids
randomly created. In Figure 2, the topographic images ob-
tained by 3-dimensional laser noncontacting profilometry for
surfaces 1 and 5 show the increase of arithmetic mean rough-
ness (Ra =114 nm for surface 1 to Ra =382 nm for surface 5).
The data collected for all the surfaces are summarized in
Table 1 and show a gradual increase of the measured rough-
ness after each bilayer addition.
(39) Synytska, A.; Ionov, L.; Dutschk, V.; Stamm, M.; Grundke, K. Langmuir
2008, 24, 11895.

11076 DOI: 10.1021/la901369f Langmuir 2009, 25(18), 11073–11077

Amigoni et al. Article

Table 1. Surface Characterisation of the Samples after Reaction with

the Aldehyde F
surfaces θaa θrb Hc f2d Ra (nm)e

0F 113 71 42 0 50
1F 120 92 28 0.34 114
2F 137 111 26 0.55 119
3F 154 129 25 0.78 243
4F 152 131 21 0.81 359
5F 151 139 12 0.84 382
a
Advancing contact angle with water ((3°). b Receding contact angle
with water ((3°). c Hysteresis. d Fraction of the water-air contact area.
e
Arithmetic mean roughness.

Figure 4. Advancing contact angle with water (]) and hysteresis

() for the fluorinated surfaces 1F (one layer of AP) to 5F (five
layers of AP).

Figure 3 represents the evolution of static contact angles with

Figure 3. Evolution of static contact angle with water (9) and
roughness (0) for the fluorinated grafted surfaces 1F to 5F (one AP
layer to five AP layers).
Influence of the Roughness on the Hydrophobicity of the
Surfaces. The surface modifications are classically revealed by
the evolution of the static and dynamic contact angles with water.
As suggested in the literature,40 the wettability of such close
packed sphere arrays may be well evaluated by the Cassie-Baxter
equation (1)41
where θ0 is the apparent water contact angle on the rough
surface, θ is the intrinsic water contact angle on the corre-
sponding flat surface, f1 is the fraction of water-solid
contact area, and f2 is the fraction of the water-air contact
area (f1 þ f2=1). As the water contact angle on the reference
flat surface 0F is 110°, f2 values can be calculated from eq 1
for the colloidal silica assemblies; the results are provided in
Table 1. f2 values increased gradually with increasing the
number of layers to reach, for surface 5F, a value as high as
f2 =0.84. Such elevated values of f2 are usually achieved by
introducing air cavities or channels on the surface mainly via
more sophisticated processes such as lithography, etching, or
phase separation.8,39,42-44
(40) Shiu, J.; Kuo, C.; Chen, P.; Mou, C. Chem. Mater. 2004, 16, 561.
(41) Cassie, A. B. D.; Baxter, S. Trans. Faraday Soc. 1944, 3, 16.
(42) Li, H.; Wang, X.; Song, Y.; Liu, Y.; Li, Q.; Jiang, L.; Zhu, D. Angew.
Chem., Int. Ed. 2001, 40, 1743.
(43) Yabu, H.; Takebayashi, M.; Tanake, M.; Shimomura, M. Langmuir 2005,
21, 3235.
(44) Shirtcliffe, N. J.; McHale, G.; Newton, M. I.; Perry, C. C. Langmuir 2003,
19, 5626.
water in parallel with the increase of roughness induced by the
successive addition of layers. We can notice a rapid evolution of
the wettability as a function of the number of layers and the
roughness. A plateau is reached for surfaces 4F and 5F, attesting a
good compromise between the number of layers and the macro-
scopic properties desired.
Furthermore, it is apparent that the higher the number of layers
the lower the hysteresis (Table 1 and Figure 4). It can be correlated
to the increase of the roughness all along the layer additions to
aim toward a nonadhesive Cassie-Baxter state.41 The low values
of hysteresis reached (3F: 25°; 4F: 21°; and 5F: 12°) are a sign of
the stability of the F monomolecular layer at the surface and
reflect a good homogeneity of the coating.
Conclusions
Five surfaces were constructed by the successive covalent graft-
ing of functional nanoparticles (AP: 295 nm diameter; EP: 20 nm
diameter), commercially available or readily synthesized by the
Str€ober process, onto a glass support previously chemically mod-
ified by the reaction of 3-glycidoxypropyltrimethoxysilane. The
natural erratic distribution of the nanoparticles onto the support
induced a nanoroughness and porosity known to be able to present
superhydrohobic properties after a further step of hydrophobiza-
tion. This step was provided by the reaction between the amino
groups of the last layer of AP and a novel designed highly
fluorinated aldehyde. It has been demonstrated that the water
repellence properties increase with the number of layers to reach
superhydrophobic surfaces (static contact angle with water >150°
and a hysteresis of 12°). Moreover, this covalent layer by layer
assemblies of silica nanoparticles lead to stable high surface area
materials that can be easily functionalized by a large number of
other active molecules than the hydrophobic precursor used in the
present study. Therefore, it is believed that this work offers new
short-term prospects for the fabrication of highly active materials
in technologies such as catalysis, sensing, or antibacterial surfaces.
Acknowledgment. This work was supported by the “Region
PACA” Council, and we acknowledge support from the society
“Bou
ee L
eo” for its contribution to the grant.
Supporting Information Available: ATR-IR spectrum of
surface 5F and SEM images of all surfaces. This material is
available free of charge via the Internet at http://pubs.acs.org.

Langmuir 2009, 25(18), 11073–11077 DOI: 10.1021/la901369f 11077