pss a
solidi
phys. stat. sol. (a) 205, No. 10, 2437 – 2440 (2008) / DOI 10.1002/pssa.200723556
Polymer microfibers obtained using
porous silicon templates
L. F. Marsal*, 1, P. Formentín1, R. Palacios1, T. Trifonov2, J. Ferré-Borrull1, A. Rodriguez2, J. Pallarés1,
and R. Alcubilla2
1
Nano-Electronic and Photonic Systems, Departament d’Enginyeria Electrònica, Elèctrica i Automàtica, Universitat Rovira i Virgili,
Av. Països Catalans 26, 43007 Tarragona, Spain
2
Departament d’Enginyeria Electrònica, Universitat Politècnica de Catalunya, Edifici C4, Campus Nord, Jordi Girona 1 – 3,
08034 Barcelona, Spain
Received 12 November 2007, revised 3 April 2008, accepted 11 June 2008
Published online 15 August 2008
PACS 81.05.Lg, 81.05.Rm, 82.35.Gh, 82.45.Vp
*
Corresponding author: e-mail lluis.marsal@urv.cat, Phone: + 34 977 559 625, Fax: + 34 977 559 605
The deposition of specific materials into ordered pores ar-
ranged in a regular lattice allows the fabrication of ordered
fiber arrays. Porous silicon is an attractive candidate for use
as a template because the porosity and pore size can be tuned.
Polymer microfibers using macroporous silicon with various
pore depths as template system is reported here. The method
entails vacuum infiltration of a polymer solution into the
1 Introduction In recent years, the fabrication of
nanostructures and microstructures based on porous tem-
plates has been intensively investigated [1–4]. The deposi-
tion of specific materials into porous templates allows
tailoring structures as inverse replicas of the pores. Fur-
thermore, the use of regular lattices of pores allows the
fabrication of ordered fiber arrays. Porous silicon is an at-
tractive candidate for use as a template because it can be
fabricated with high precision and uniformity in a large
scale and because the porosity and average pore size and
pore depth can be tuned by adjusting the electrochemical
preparation techniques [5–8]. One interesting application
for these structures is the infiltration of the air holes with
an organic material such as polymers, which are favoured
in many applications because many of them are transparent,
compliant, and biocompatible and/or biodegradable. In
addition, polymer devices are inexpensive and disposable.
In order to be suitable as templates for the preparation
of microfibers, porous substrates must have pore walls
with a high surface energy. Inorganic oxides such as sili-
con oxide, meet this requirement and organic polymers are
among the materials with low surface energy [9]. Polymer
physica
status
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applications and materials science
pores of the template. Two different types of polymer were
selected in order to obtain ordered arrays of fibers made from
Poly(methyl) methacrylate) or Poly(dimethylsiloxane). Mi-
crotubes were obtained when we used a silicon membrane as
a template, whereas microfibers were obtained when we used
a silicon template with pores opened only at one end.
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
melts are molten onto templates in excess, whereas wetting
with polymer solutions occurs dropwise under ambient
conditions [10]. With polymer melts as well as polymer so-
lutions the pore walls are completely wetted, with com-
plete reproduction of the pore structure. The liquid film so
solidifies when cooled or the solvent is evaporated leading
to crystallization or vitrification.
We have used a vacuum infiltration for the fabrication
of ordered arrays of polymer microstructures with a mono-
disperse size distribution and uniform orientation using po-
rous silicon substrates. We will investigate how the type of
template, the aspect ratio (depth/diameter) of the pore and
the properties of the polymers influence the microstruc-
tures fabrication. To this end, we used silicon templates
with a pore diameter of 2–3 μm and various pore depths
from 7.5 μm to 150 μm. The polymers employed were
Poly(methyl) methacrylate and Poly(dimethylsiloxane).
2 Experimental Ordered macroporous silicon was
prepared by light-assisted electrochemical etching [11, 12].
The starting material was n-type silicon with a resistivity
of 2–3 Ω cm. The front side of the wafers was patterned
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
 pss a

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2438 L. F. Marsal et al.: Polymer microfibers obtained using porous silicon templates

with inverted pyramid shaped pits by oxidation, photo- ad d

a
lithography, and subsequent tetramethyl ammonium hy-
droxide (TMAH) etching. These inverted pyramids act as
nucleation sites for the ordered pore growth. The wafers
were incorporated in an electrochemical etching cell con-
taining a 5 wt% aqueous solution of HF acid at low tem-
perature. The quality and size of the pores were controlled b
e eb
by a computerized feedback mechanism to maintain a con-
stant pore diameter. Samples with a pore depth (Tp) be-
tween 7.5 μm and 22 μm and pore diameter (Dp) between
2 μm and 3 μm were fabricated. In order to see the effect
of the opening pore, free-standing silicon membranes were
prepared as well, where after pore growth the back side of
the wafer was etched until the pores were opened. In this
case porous silicon membranes with 150 μm of pore depth
were obtained. cf fc
Polymer microtubes and polymer microfibers using
Figure 1 Schematic diagram of a) – c) infiltration process using
silicon membranes or structures open only at one end were
silicon membrane and d) – f) infiltration process using silicon sub-
fabricated by vacuum infiltration of 15 wt% polymer in strates open only at one end. A polymer solution is placed on the
toluene. PMMA (Poly(methyl)methacrylate, Mw = 120000 surface of the silicon template (a) and (d). A mesoscopic film of
purchased from Sigma-Aldrich) and PDMS (Poly(di- the liquid wets the pore walls in order to form tubular structures
methylsiloxane), Sylgard 184, Dow Corning) which was (b). Polymer microfibers form as replicas of the template pores
prepared by thoroughly mixing and degassing a 10:1 ratio (e). Polymer microfibers and polymer microtubes after removing
of liquid silicon base and a curing agent, were selected as a templates (c) and (f).
polymeric material.
The technique was an infiltration by putting a drop of Polymethylmethacrylate (PMMA) is a versatile mate-
the solution on top of the sample located under vacuum. rial which has been used in a wide range of fields and ap-
The samples were heated at 110 °C during 3 h, followed by plications. It is often used as an alternative to glass al-
an immersion into 40 wt% KOH (aq) at 40 °C in order to though there are some differences between the polymer
remove the silicon templates. and the glass. PMMA is less dense, has higher impact
All the samples were inspected in environmental scan- strength and is softer and more easily scratched than
ning electron microscopy (ESEM) using a ESEM-FEI
Quanta 600 operated at an accelerating voltage of
10–15 kV. a
b

3 Results and discussion Ordered porous silicon

substrates with pore walls covered with a native silica layer
were used as template. They had a high surface energy
compared to that of organic liquids such as polymer melts
[13]. Under these conditions and provided that the wetting
temperature is sufficiently high, a mesoscopic polymer
film of a few tens of nanometers rapidly covers the pore
walls; the solidification of this film yields tubular micro-
fibers with a length corresponding to the depth of the c d
template pores. Microtubes are obtained when the template
used is a silicon membrane. The interior of the pore has
not been completely filled by the polymeric solution
(Fig. 1b, c). However, if the ordered macroporous template
is open only at one end, a complete filling of the pore oc-
curs. In this case polymer microfibers as replicas of the
template pores are obtained (Fig. 1e, f) [4, 10, 14].
Membranes with a pore diameter of 3 μm and a pore
depth of 150 μm, and substrates open only at one end with a Figure 2 a) and b) ESEM micrographs of macroporous silicon
pore diameter value of 2 μm and various pore depth values membrane with a pore diameter of 3 µm and a pore depth of
from 7.5 μm to 22 μm prepared according to procedures de- 150 µm, top view and cross section. c) and d) SEM micrographs
scribed previously, were employed in this work. The pores of macroporous silicon structure open only at one end with a pore
of these Si substrates are very uniform in size as Fig. 2 shows. diameter of 2 µm and a pore depth of 22 µm.

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 Original
Paper

phys. stat. sol. (a) 205, No. 10 (2008) 2439

a b
a

Figure 3 ESEM images of PMMA microtubes detached from

b
macroporous Si membrane with 150 µm of pore depth. a) Cross-
sectional and b) top view of the microtubes.

glass. Unlike glass, PMMA does not filter ultraviolet light.

PMMA transmits UV light down to 300 nm and allows in-
frared light of up to 2800 nm wavelength to pass.
Figure 3 shows PMMA microtubes after removing the
template with a pore depth value of 150 μm. In the figure
is shown the uniform high aspect ratio and the tubular form
of these polymeric structures because of the template em- c
ployed (Fig. 1a–c).
In order to investigate the formation of the microtubes,
different concentrations of the PMMA have been studied.
Results show that the amount of the polymer does not af-
fect the preparation of the microtubes. Experiments with
5 wt% and 30 wt% PMMA solution were carried out and
microtubes with 150 μm of lengths and similar morphol-
ogy to the 15 wt% PMMA were obtained. However, when
the infiltration was at ambient atmosphere the filling of Figure 5 ESEM images of PMMA microfibers. Cross-sectional
the pore is similar but the microtubes walls are different. and top views of microfibers after removing the template with
Figure 4 shows how the walls of the tube are thicker pore depth values of a) 22 µm, b) 17.5 µm and c) 7.5 µm.
when the microtube is prepared at ambient atmosphere,
probably because of the evaporation of the solvent under
Free-standing microfibers can be produced by using
vacuum.
silicon templates with a pore depth less than 10 μm
In order to study the effect of the pore opened only at
(Fig. 5c). PMMA fibers start to congregate into disordered
one end, silicon templates with pore depths of 7.5 μm,
domains if the pore depth value is higher than 15 μm and
17.5 μm and 22 μm were employed.
this problem increase if the template posses pores with
The PMMA microfibers released from templates pos-
more than 20 μm in depth (Fig. 5a).
sess caps with hemispherical shape, indicating that the mi-
We have also investigated different conditions with
crofibers are replicas of the pore bottoms (Fig. 1d–f). In the
these structures opened only at one end. The results were
ESEM images (Fig. 5) they might appear shorter because
similar to the previously obtained with silicon membranes.
the fibers are tilted. Geometrical effects will lead to an ap-
Results seem that the concentration of the polymer solution
parent length of the fibers different from their actual length.
does not influence the filling of the pore. However, if the
PMMA microfibers are prepared at ambient atmosphere,
a b the length of the fiber decreases.
Poly(dimethylsiloxane) (PDMS) was selected as a soft
model polymer to fabricate ordered microfibers. PDMS is
used in a variety of products, partly because of its unique
properties but also it is a relatively cheap material. PDMS
is inert, resistant to wet, ozone, UV and gamma radiation,
has a low surface tension and high surface activity.
Figure 6 shows PDMS microfibers obtained with a
silicon membrane as template. The picture shows the soft-
Figure 4 ESEM images of a) cross-sectional and b) top view of ness of the polymer. The microfibers are apparently solid,
the PMMA microtubes. The walls of the tube are 3 times more even though the template employed was a membrane,
wide when the preparation is carried out at ambient conditions. probably because of the properties of the PDMS.

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 pss a
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2440 L. F. Marsal et al.: Polymer microfibers obtained using porous silicon templates
a b
Figure 6 a) Cross-sectional and b) top view ESEM images of
PDMS microfibers after removing the template by immersion
into KOH (aq).
Si structures open only at one end were infiltrated with
PDMS as well, using the same pore depth values that we
had used previously for PMMA. In this case we could not
eliminate template without damaging the polymer. Al-
though it is compatible with some inorganic bases [15],
PDMS is melted when the silicon is removed by KOH (aq)
at 40 °C. The microfibers are formed but they cannot stay
standing, they tend to bend due to the polymer softness.
Following these results, we can conclude that the PDMS is
not a good material to obtain ordered microfibers with our
conditions for eliminating silicon templates, it would be
better to use rigid polymers as acrylic polymers, such as
PMMA.
4 Conclusions Polymer microtubes or polymer mi-
crofibers depending on the template have been fabricated
using vacuum infiltration. Microtubes were obtained when
the template was a silicon membrane and the microfibers
were obtained when the template used was a silicon sub-
strate opened only at one end.
We have studied how the type of template, the aspect
ratio of the pore, the filling of the pore and the properties
of the polymers, PMMA or PDMS, influence the micro-
tubes and microfibers preparation.
Results show that PDMS is not a good material to ob-
tain ordered microfibers or microtubes. Only solid mi-
crofibers were obtained with this material which tends to
bend because of the polymer softness.
This work can be extended to different types of polymers
such as conductive or luminescent compounds or employing
other materials as templates with smaller dimensions.
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Acknowledgements This work was supported by Spanish
Ministry of Education and Science (MEC) under grant number
TEC2006-06531 and HOPE CSD2007-00007 (Consolider-
Ingenio 2010). Josep Ferré-Borrull acknowledges the Ramón y
Cajal fellowship from the Spanish Ministerio de Ciencia y Tec-
nología. Trifon Trifinov acknowledges support from the Spanish
Goverment for a Juan de la Cierva fellowship.
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