Materials Science and Engineering C 23 (2003) 13 – 18

www.elsevier.com/locate/msec

Fabrication of miniaturised Si-based electrocatalytic membranes

G. D’Arrigo a,*, C. Spinella a, G. Arena b, S. Lorenti b
a
CNR-IMETEM, Stradale Primosole 50, 95121 Catania, Italy
b
STMicroelectronics, Stradale Primosole 50, 95121 Catania, Italy

Abstract

The increasing interest for light and movable electronic systems, cell phones and small digital devices, drives the technological research
toward integrated regenerating power sources with small dimensions and great autonomy. Conventional batteries are already unable to deliver
power in more and more shrunk volumes maintaining the requirements of long duration and light weight. A possible solution to overcome
these limits is the use of miniaturised fuel cell. The fuel cell offers a greater gravimetric energy density compared to conventional batteries.
The micromachining technology of silicon is an important tool to reduce the fuel cell structure to micrometer sizes. The use of silicon also
gives the opportunity to integrate the power source and the electronic circuits controlling the fuel cell on the same structure. This paper
reports preliminary results concerning the micromachining procedure for fabricating a Si-based electrocatalytic membrane for miniaturised
Si-based proton exchange membrane fuel cells (PEMFC).
D 2002 Elsevier Science B.V. All rights reserved.

Keywords: Microchannel fabrication; Porous membrane; Fuel cell; Nafion impregantion

1. Introduction tioned above a microchannel system using only surface

micromachining, fully compatible with the standard ULSI
Fuel cells typically consist of an electrolyte material silicon technology. The results of the present work refer to
based on either polymer (proton exchange type) or solid the fabrication steps of one single half element of a mini-
oxide materials, which are encapsulated between electro- aturised Si-based fuel cell.
des. The fuel cell operates when fuel (usually hydrogen) is
delivered to one electrode, and oxygen to the other. By
heating the electrode – electrolyte structure, fuel and oxi- 2. Experiments and results
dant diffuse toward the interface of one electrode encoun-
tering the catalytic material. An electrocatalytic reaction The scheme of the complete structure is depicted in Fig.
can then occur releasing free electrons, which are collected 1. We start by the realisation of microchannels for the
and used in an external circuit, while ions flow across the uniform distribution of oxygen and fuel. Then we form
electrolyte membrane towards the other electrode to form the electrocatalytic membrane above the microchannel by
water. electrolytic deposition of catalytic element in a silicon
Miniaturised electrocatalytic membranes integrated on Si porous structure formed above the microchannels. Finally,
by using micromachining processes have emerged recently all the porous layers are impregnated with the polymeric
as a possible way to fabricate miniaturised Si-based proton proton exchange membrane. All the experiments were
exchange membrane fuel cells (PEMFC) for mobile appli- performed on lowly doped p-type Czochralski Si (001)
cations [1]. The aim of this work is to introduce an wafers.
innovative micromachining procedure, using advanced and We now discuss the above-listed technological steps in
smart material engineering, to fabricate electrocatalytic detail.
porous membranes, with wide and tuneable surface, posi-
2.1. Formation of microchannels

* Corresponding author. Tel.: +39-95-591212; fax: +39-95-7139154. For the formation of microchannels, we started from
E-mail address: giuseppe.darrigo@imm.cnr.it (G. D’Arrigo). the realisation of deep trenches on the silicon wafer. For

0928-4931/02/$ - see front matter D 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 8 - 4 9 3 1 ( 0 2 ) 0 0 2 2 8 - X
14 G. D’Arrigo et al. / Materials Science and Engineering C 23 (2003) 13–18

exposed to anisotropic KOH etch using a water solution

at 33% at a temperature of 50 jC for 15 min. It is well
known that KOH [2,3] or TMAH solutions etch silicon
with etching rate strongly depend on the different crystal-
line orientations. This property is particularly useful to
fabricate 3D micromachined structures by highly control-
lable and reproducible way. After the anisotropic etch, the
trench structure modifies assuming the shape shown in
Fig. 3. Fig. 3a is a SEM micrograph of a single trench
after KOH etch, while Fig. 3b refers to a sequence of
more trenches defined on the same wafer. We note that the
original trench walls are now converted in a couple of
rotated v-grooves defining a rhombohedral microchannel
–
structure. This shape is produced because, at the [11 0]
trench walls, the etch of silicon proceeds with the highest
etching rate of the (001) planes until the slowly etched
Fig. 1. Schematic description of Proton Exchange Fuel Cell structure. It is (111) planes meet the above hard mask and meet each
formed by two symmetric half elements. A polymeric ion conducting other inside the silicon substrate. After this instant, the
membrane is positioned between the two half elements. The arrays of etch can continue with the slow etching rate of the (111)
microchannels shown are used to transport the fuel, hydrogen or methanol, planes. This process leaves the top of each microchannel
on one half element, and the oxygen on the other, towards the porous
catalytic membrane. We will consider the fabrication of single half element
open as shown in Fig. 3a. In order to close this aperture,
circled with the black rectangle. we performed a chemical vapour deposition (CVD) of p+
epitaxial silicon after the hard mask removal. The depo-
sition temperature was 1080 jC using B2H6 and SiH2Cl2
this aim, we used a standard photolithography process. A and the deposition time was 200 s for a final epitaxial
silicon nitride layer, 140 nm thick, was deposited on the layer thickness of about 4.5 Am. The final result is shown
Si wafer and used as hard mask. Trenches, 8 Am deep and in Fig. 4. For comparison, the dashed line defines the
1 Am wide, were defined by reactive ion etching. These profile of the rhombohedral cavity before the deposition.
trenches, one of which is shown by the scanning electron We note that the epitaxial growth is conformal along the
microscopy (SEM) image in Fig. 2, extend along the inner walls of the microchannel. The thickness of this
h110i direction of the Si wafer and their inner walls are inner epitaxial layer is equal to half of the initial aperture
–
parallel to the [11 0] planes. The trench structure was present on top of the microchannel.

Fig. 2. Scanning electron microscopy (SEM) image of trenches structures. The trenches are extended along the h110i direction of the Si wafer and their inner
walls are parallel to the [110] planes.
 G. D’Arrigo et al. / Materials Science and Engineering C 23 (2003) 13–18 15

Fig. 3. (a) SEM micrograph of a single trench after the anisotropic etch obtained using a water solution at 33% of KOH etch at 55 jC, while (b) refers to a
sequence of more trenches defined on the same wafer.

2.2. Formation of a porous electrocatalytic membrane addition of a solvent (isopropyl alcohol) [4]. The electro-
chemical cell was maintained in a galvanostatic configu-
Fig. 5 is a plot of the carrier concentration profile of the ration, i.e. at a fixed current equal to 22 mA/cm2 for a time
deposited silicon. It is characterised by a plateau at a of 300 s. Fig. 6 is a SEM micrograph showing the structure
concentration of 1  1019 cm 3 terminating with a quite of the porous silicon layer which extends for all the p+
abrupt interface with the silicon substrate. The concentra- epitaxial silicon layer. The wide surface of the mesoporous
tion level of the deposited layer allows us to obtain a silicon structure can be effectively used to trap Pt and Ru
mesoporous silicon structure by electrochemical etching catalytic element to form a catalytic membrane. The inser-
using a solution containing a HF/H2O mixture with the tion of Pt or Ru inside the porous Si was obtained by
16 G. D’Arrigo et al. / Materials Science and Engineering C 23 (2003) 13–18

Fig. 4. SEM micrograph of the final result after the chemical vapour deposition (CVD) of p+ epitaxial silicon. The deposition temperature was 1080 jC using
B2H6 and SiH2Cl2. The dashed line defines the profile of the rhombohedral cavity before the deposition. We note that the epitaxial growth is conformal along
the inner walls of the microchannel. The thickness of this inner epitaxial layer is equal to half of the initial aperture present on top of the microchannel.

electrodeposition using a potentiostatic/galvanostatic sys- was positioned as working electrode in the cell exposing
tem, a tree electrode cell and water solution of 1.0 M only the porous surface to the solution; the deposition was
H2SO4 + 16 mM H2PtCl6 and 8 mM K2RuCl5. The sample achieved by pulsing the working electrode potential versus
the reference electrode [1]. Fig. 7 is a micrograph of a
portion of the porous Si layer after the Pt electrodeposition
obtained by transmission electron microscopy (TEM).
Metal catalytic clusters are clearly visible as dark spots
dispersed in the porous silicon structure.

2.3. Impregnation with the polymeric proton exchange

membrane

The PEMFC half element was completed by the impreg-

nation of the silicon mesoporous catalytic layer with a

Fig. 5. Carrier concentration profile of the deposited epitaxial silicon layer.

It is characterised by a plateau at a concentration of 1  1019 cm 3 Fig. 6. SEM micrograph showing the structure of the porous silicon layer
terminating with a quite abrupt interface with the silicon substrate. which extends for all the p+ epitaxial silicon layer.
 G. D’Arrigo et al. / Materials Science and Engineering C 23 (2003) 13–18 17

shown in Fig. 8. Fig. 8a is the standard TEM micrograph of

the sample containing Nafion in contact with the porous
silicon layer. Fig. 8b and c are the EFTEM maps of
elemental C and F, respectively, on the same sample region.
From these maps, we observe that both C and F are present
within the porous Si structure. The integration of the

Fig. 7. TEM micrograph of a portion of the porous Si layer after the Pt

electrodeposition obtained by electrodeposition using a water solution of
H2SO4 + H2PtCl6 and K2RuCl5. Metal catalytic clusters are clearly visible,
some of them are indicated with arrows, as dark spots dispersed in the
porous silicon structure.

polymeric proton exchange membrane [5]. We used a fully

hydrated and protonated Nafion 117 membrane (Aldrich),
containing deionised water and isopropyl alcohol. This
liquid solution was spun onto the sample surface. After 1
h at room temperature, the polymeric film stabilises. In
order to investigate the degree of absorption of Nafion by
the porous Si structure, we performed energy filtered TEM
(EFTEM) analyses using a JEOL JEM 2010F microscope
equipped with a field emission gun and with the Gatan
electron energy loss image filter (GIF). The filter allows us
to acquire maps of the chemical elements present in the
samples with a high spatial resolution (0.19 nm). The
EFTEM analysis of elemental F and C present in the Nafion
structure was performed by the three windows background
subtraction method [6]. To obtain an energy filtered map of
fluorine, the FK 685 eV electron energy loss edge was
employed, with a post-edge 30 eV window placed at 700
eV and pre-edge windows placed at 637 and 667 eV. While Fig. 8. (a) Standard TEM micrograph of the sample containing Nafion in
contact with the porous silicon layer. (b) and (c) are the EFTEM maps of
for carbon, we used the CK 284 eV electron energy loss elemental C and F, respectively, on the same sample region. From these
edge, with a post-edge 20 eV window placed at 294 eV and maps, we observe that both C and F are present within the porous Si
pre-edge windows placed at 252 and 272 eV. Results are structure.
18 G. D’Arrigo et al. / Materials Science and Engineering C 23 (2003) 13–18

electron energy loss signal of C or F over the total observed and oxidation chemical reactions responsible of the energy
area allowed us to conclude that the amount of C and F production.
incorporated in the porous Si is about 35% of the one
present in the surface Nafion layer. This number is consis-
tent with the porosity of the porous Si layer demonstrating Acknowledgements
that Nafion is uniformly filling all the holes present in the
porous structure. We would like to acknowledge Markus Italia for
performing the spreading resistance analysis, Corrado
Bongiorno and Salvatore Pannitteri for the TEM analysis
3. Conclusions and Antonio La Mantia for SEM analysis.

In conclusion, we have demonstrated that surface micro-

References
machining of silicon is a technology which allows us to
realise all the components of miniaturised fuel cells: micro- [1] S.C. Kelley, et al., Electrochem. Solid-State Lett. 3 (9) (2000) 407 – 409.
channels, electrocatalytic membranes, and the integration of [2] H. Seidel, et al., J. Electrochem. Soc. 137 (11) (November 1990)
the polymeric proton exchange membrane. 3612 – 3625.
Porous silicon is demonstrated to be an effective mate- [3] H. Seidel, et al., J. Electrochem. Soc. 137 (11) (November 1990)
rial to incorporate Nafion which can easily diffuse through 3626 – 3632.
[4] V. Lehman, Electrochemistry of Silicon, Wiley-VCH, 2002.
the porous structure, containing the catalyst elements. Due [5] S.R. Narayanan, et al., The Electrochemical Society Proceedings Ser-
to the large surface/volume ratio, porous silicon is an ies, Pennington, New Jersey, 1995, p. 261.
attractive material to optimize the yield of the reduction [6] O.L. Krivenec, et al., Mater. Res. Soc. Symp. Proc. 332 (1994) 341.