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A Nanoporous Silicon Membrane Electrode Assembly for On-Chip Micro Fuel

Cell Applications

Article  in  Journal of Microelectromechanical Systems · July 2006

DOI: 10.1109/JMEMS.2006.872223 · Source: IEEE Xplore

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JOURNAL OF MICROELECTROMECHANICAL SYSTEMS, VOL. 15, NO. 3, JUNE 2006 671

A Nanoporous Silicon Membrane Electrode Assembly

for On-Chip Micro Fuel Cell Applications
Kuan-Lun Chu, Scott Gold, Vaidyanathan (Ravi) Subramanian, Chang Lu, Mark A. Shannon, and Richard I. Masel

Abstract—Silicon-based fuel cells are under active development

for chip-scale electrical power supply. One of the greatest chal-
lenges in micro-fuel-cell research is the development of a suitable
proton conducting membrane material that is compatible with
standard silicon microfabrication technology. In this paper, the
use of nanoporous silicon as a novel proton conducting membrane
material in a microscale fuel cell membrane electrode assembly
(MEA) is demonstrated. The devices were fabricated by first
creating 100- m-thick silicon windows in a standard silicon
wafer, anodizing to create pores in the windows, and then painting
catalyst layers and insulators onto the porous structures. Using
5 M formic acid and 0.5 M sulfuric acid as the fuel, the fuel
cell peak power density reached about 30 mW/cm2 at current
density level of about 120 mA/cm2 . These results represent the
successful integration of a new class of protonic conductor into a
microfabricated silicon fuel cell. [1455]
Index Terms—Micro fuel cells, porous silicon.
Fig. 1. An illustration of the fabrication scheme used to create the porous
I. INTRODUCTION silicon membranes.

T HERE has recently been considerable interest in devel-

oping silicon-based micro fuel cells for chip scale power
[1]–[5]. Fuel cells have several advantages over traditional bat-
teries, including rapid recharging and much higher energy den-
sities. Among the many types of fuel cell systems, proton ex-
change membrane fuel cells (PEMFC) have been most widely
examined as major future power sources for microscale devices.
Significant efforts have focused on the development of CMOS
compatible processes and materials to produce silicon-based
PEMFCs that can be integrated with microelectronic and mi-
croelectromechanical systems (MEMS) devices.
Development of a suitable proton conducting membrane
material has proved to be one of the greatest challenges in the
manufacture of micro fuel cells. Nafion or a similar polymer
is most widely used as a proton conductor in silicon micro
fuel cells and in PEMFCs in general. However, Nafion is not

Manuscript received November 4, 2004; revised September 10, 2005. This
work was supported by the Defense Advanced Research Projects Agency under
U.S. Air Force Grant F33615-01-C-2172. Subject Editor J. Judy.
K.-L. Chu, V. Subramanian, and R. I. Masel are with the Department
of Chemical and Biomolecular Engineering, University of Illinois at Ur-
bana-Champaign, Urbana, IL 61801 USA (e-mail: r-masel@uiuc.edu).
S. Gold was with the Department of Chemical and Biomolecular Engineering,
University of Illinois, Urbana, IL 61801 USA. He is now with the Chemical En-
gineering Program and Institute for Micromanufacturing, Louisiana Tech Uni-
versity, Ruston, LA 71270 USA.
C. Lu was with the Department of Chemical and Biomolecular Engineering,
University of Illinois, Urbana, IL 61801 USA. He is now with the Agricultural
and Biological Engineering, Purdue University, West Lafayette, IN 47907-2093
USA.
M. A. Shannon is with the Department of Mechanical and Industrial Engi-
neering, University of Illinois, Urbana, IL 61801 USA.
Digital Object Identifier 10.1109/JMEMS.2006.872223
1057-7157/$20.00 © 2006 IEEE
Fig. 2. Nanoporous silicon formation setup for fabrication step in Fig. 1(f).
readily integrated with standard microfabrication techniques
used in making micro fuel cells, other microchemical systems,
or MEMS-based devices, as it cannot be easily patterned using
photolithography and bonding it to silicon and other commonly
used materials is extremely challenging under working fuel
cell conditions due to its volumetric changes with changes
in hydration level [6]. Countless efforts have been made to
develop a next-generation protonic conducting membrane ma-
terial to replace Nafion. Solid-state protonic conductors include
materials such as solid acids, polymers, oxide ceramics, and
intercalation compounds [7], [8]. One common approach has
672 JOURNAL OF MICROELECTROMECHANICAL SYSTEMS, VOL. 15, NO. 3, JUNE 2006

(a) (b)
Fig. 3. SEM image of nanoporous silicon membrane (cross section view) at (a) low magnification and (b) high magnification.

Fig. 4. SEM image of porous silicon (top face view). Fig. 5. An illustration of the fuel cell as tested.

been to use inorganic–organic hybrid materials, often including

Nafion as one of the components. Examples of such composite
proton conducting membrane materials reported in the litera-
ture include Nafion-silica [9]–[11], Nafion-borosiloxane [12],
and silica-polyethylene oxide [13] composites, among others.
More recently, nanoporous silicon has been shown to have
strong potential as a proton conducting fuel cell membrane
material having proton conductivity and fuel crossover flux
comparable to Nafion [14], [15]. Nanoporous silicon, which
is readily formed by anodic etching in hydrofluoric acid, is
compatible with conventional Si microfabrication technologies,
presenting the possibility of fabricating different components
of a fuel cell or even a fuel cell and its supported devices in a
Fig. 6. SEM image of the nanoporous TiO layer on the anode side of the
device.
monolithic fashion. Nanoporous silicon should also be stable at
elevated temperatures, unlike many polymeric materials. II. EXPERIMENTAL METHODS
The objective of this paper is to demonstrate the potential
of nanoporous silicon as a protonic conductor in a silicon A. Nanoporous Silicon Membrane Fabrication
micro fuel cell. In the study reported in this paper, a membrane The procedure used to fabricate the nanoporous silicon mem-
electrode assembly (MEA), a crucial component of almost all branes is illustrated in Fig. 1. Generally, the procedure was to
fuel cell systems, was fabricated using nanoporous silicon. use deep reactive ion etching (DRIE) to form 100 M mem-
The performance of this MEA was evaluated by measuring its branes in a standard silicon wafer. The membranes were then an-
current–voltage characteristics and power output. odized, to convert them to porous silicon. Then catalyst layers,
CHU et al.: NANOPOROUS SILICON MEMBRANE ELECTRODE ASSEMBLY
Fig. 7. Polarization and power density curves for two nanoporous silicon MEAs that were insulated with a
a solution containing: : 5 M formic acid plus 0.5 M sulfuric acid; euro: 5 M formic acid with no sulfuric acid.
insulators, and current collectors were painted onto the wafers
to create fuel cells.
In detail, the fabrication started with prime grade p-type
(boron-doped) double side polished 100 silicon wafers with
100 mm diameter and 0.01–0.02 -cm resistivity from Wafer
World Inc. Native oxide on the wafer surface was removed
by immersion in a buffered oxide etch (BOE) solution prior
to any other processing [Fig. 1(a)]. First, an approximately
800-nm-thick silicon nitride film was deposited on both wafer
sides by low-pressure chemical vapor deposition [Fig. 1(b)].
Photolithography was used to pattern four small circles on
the front side of each die with a total area (all four cells)
of 0.0625 cm . Each die has a square shape with 2.25 cm
area. Reactive ion etching with freon plasma was then used to
remove the silicon nitride from wafer back side and to expose
the four circles on the front side, as shown in Fig. 1(c). Silicon
membranes with thickness of 100 m were formed by DRIE
[Fig. 1(d)]. For each die, the indented side etched down by
DRIE is referred as the front side, and the opposite flat side
as the backside, in the rest of this paper. A 50 nm chrome and
gold layer was then sputtered on the backside of the wafer for
electrical contact following removal of any native oxide with
a BOE solution. AZ 4903 photoresist was spin-coated on top
of the chrome layer to protect it from acid etching in the next
673
TiO film. The measurements were done using fuel
step [Fig. 1(e)]. A nanoporous silicon membrane was formed
by immersing the die in an electrolyte solution composed of
ethanol and 49 wt.% hydrofluoric acid (1:1 by volume) stirred
by magnet rotor and passing a constant current of 40 mA/cm
through the four circular membranes, while silicon die was
the anode and a platinum wire coil acted as the cathode in
the electrolyte solution, as illustrated in Fig. 2. Nanopores
were formed by electrochemical etching of silicon. The die
with porous silicon membrane was illustrated in Fig. 1(f). The
photoresist and chrome on the die were removed by piranha
solution (1:3 volume ratio of 30 wt.% (aq): 98 wt.%
) and chrome etchant, respectively [Fig. 1(g)]. Scanning
electron microscopic (SEM) images of the nanoporous silicon
membrane surfaces and cross sections were obtained using
a Hitachi S4700 field emission gun SEM at the Center for
Microanalysis of Materials (CMM), University of Illinois at
Urbana-Champaign, and are shown in Figs. 3 and 4.
B. Construction of the Fuel Cell
The final fuel cell is illustrated in Fig. 5. Generally, the fuel
cell is constructed by painting a layer onto the membrane,
adding anode and cathode catalyst layers onto the nanoporous
silicon membrane, and then insulating with a sol.
674
Fig. 8. Polarization and power density curves for two different nanoporous silicon MEAs. Both were insulated with a
identical procedures. The measurements were done using fuel a solution containing 5 M formic acid plus 0.5 M sulfuric acid.
In detail, the backside surfaces of four circular nanoporous
silicon membrane were painted by brush with nanopar-
ticle colloid to form an insulating film on top of nanoporous sil-
icon. When being painted, temperature of the silicon die was
maintained between 40 and 50 C. This insulating film is to
prevent short-circuiting between anode and cathode electrodes
formed on the two opposite sides of nonporous silicon mem-
brane in the following steps. The colloids were prepared
by the hydrolysis of titanium isopropoxide (0.6 M) ( 99%) ob-
tained from Aldrich Chemical Co. in acetic acid for 12–16 h.
The sol thus prepared was autoclaved at 230 C for 12 h and al-
lowed to cool to room temperature. An alternative to the above
method for insulating film was depositing film on the
backside surfaces of the four circular nanoporous silicon mem-
branes (and also other area on the die) by PlasmaLab plasma-en-
hanced chemical vapor deposition system. The thickness of this
film is around 6 nm. The catalysts for both anode and
cathode were prepared by ink-painting method, which is com-
monly used for macroscale fuel cell systems. The catalyst ink
for anode was prepared by mixing 10 mg of palladium black
JOURNAL OF MICROELECTROMECHANICAL SYSTEMS, VOL. 15, NO. 3, JUNE 2006
TiO film. Both were fabricated with
powder (Sigma-Aldrich), 40 mg of 5% Nafion solution (Solu-
tion Technology Inc.), and 100 mg Millipore , and then son-
ication for 1 min. This catalyst ink for the anode was painted by
brush on top of the insulating film, which is or thin
film on the back side of the porous silicon membrane. The ink
for cathode was prepared by mixing 10 mg of platinum black
powder (Alfa-Aesar), 40 mg of 5% Nafion solution, and 100 mg
Millipore , and sonication for 1 min. The catalyst ink for
the cathode was painted by brush on the front side surfaces of
the porous silicon membranes. To make the anode catalyst layer
surfaces hydrophilic so that fuel can be attracted to the catalyst
to facilitate anode reaction, an additional thin film was
painted by brush on top of the palladium film. The complete
nanoporous silicon membrane electrode assembly is illustrated
in Fig. 5.
C. Micro Fuel Cell Performance Testing
Nanoporous silicon membrane electrode assembly was tested
by dropping about 50 of fuel solution on the anode side of
CHU et al.: NANOPOROUS SILICON MEMBRANE ELECTRODE ASSEMBLY
Fig. 9. Polarization and power density curves for two different nanoporous silicon MEAs. Both were insulated with a
identical procedures. The measurements were done using fuel a solution containing 5 M formic acid plus 0.5 M sulfuric acid.
silicon die, which was held horizontally. The fuel solution was
either 5 M formic acid or 5 M formic acid with 0.5 M sulfuric
acid. The formic acid/sulfuric acid mixture is quickly wicked
into the and catalyst layers but does not flow through
the porous silicon. The testing setup is illustrated with the
nanoporous silicon MEA structure in Fig. 5. In all tests, the
cathode was air-breathing.
III. RESULTS AND DISCUSSION
SEM images of the nanoporous silicon membranes are shown
in Figs. 3 and 4. Generally, the films contain branched, inter-
connected pores with an average diameter of less than 10 nm.
The SEM images of the thin film (Fig. 6) and the catalyst
layers show that they are also porous.
The polarization curves (voltage–current density curves) for
nanoporous silicon MEA with insulating film were taken
using two kinds of fuel solutions, as illustrated in Fig. 7(a). One
of the fuel solutions is 5 M formic acid and the other is 5 M
formic acid plus 0.5 M sulfuric acid, in which formic acid is
675
SiO film. Both were fabricated with
the fuel oxidized at the anode. Open cell potentials (the voltage
output of MEA in the zero current density limit) shown by both
curves in Fig. 7 were much lower than the theoretical electromo-
tive force of formic acid fuel cell, which is 1.45 V, and also lower
than Nafion membrane-based MEA, which is usually 1.0 V. This
is attributed to higher fuel crossover through the membrane from
the anode side to the cathode side in nanoporous silicon mem-
brane than in Nafion membrane [14]. This is also the evidence
that fuel solution penetrated into the MEA from the top
film, the anode catalyst layer, insulating film, and into the
pores of the nanoporous silicon membranes. Fuel solution inside
the pores contributed to proton conductivity of the membrane. It
can be seen from both Fig. 7(a) and (b) that nanoporous silicon
MEA showed better performances when 0.5 M sulfuric acid was
added in the fuel solution than when just using 5 M formic acid
alone as fuel. This improvement in performances is attributed to
increase in proton conductivity (contributed by sulfuric acid) of
fuel solution inside the pores of nanoporous silicon membranes.
Therefore in the following figures, all data were obtained by
using fuel solution of 5 M formic acid plus 0.5 M sulfuric acid.
676
In order to explore the reproducability of the findings, Figs. 8
and 9 show polarization curves and power density curves for
nanoporous silicon MEAs made in two different batches. It can
be seen that there were differences in their performances though
they were prepared with the same procedure. The MEA with
higher open cell potential also has lower short-circuit current
density (the current density output when anode and cathode are
short-circuited). This is as expected if there were slight differ-
ences in the proton conductivity in the porous silicon the two dif-
ferent batches of porous silicon membranes. Physically, as the
conductivity of the membrane decreases, the parasitic currents
due to fuel transport through the membrane are reduced. That
raises the open cell potential. Unfortunately, the proton conduc-
tivity is reduced. That reduces the short circuit current.
At this point we are not completely clear why the batch-to-
batch variations in the conductivity of the membranes exists. In
our pervious paper [15], we noted that the anodization of the
porous silicon stops when the chrome on the backside of the
membrane dissolves. That can result in incomplete anodization
of the membrane where some of the pores do not extend com-
pletely through the membrane.
IV. CONCLUSION
In this paper, nanoporous silicon is demonstrated to be a
novel proton conducting membrane material for membrane
electrode assemblies in a microscale silicon fuel cells. With 5
M formic acid as the fuel and 0.5 M sulfuric acid added to the
fuel to increase proton conductivity, the fuel cell peak power
density reached about 30 mW/cm at current density of about
120 mA/cm .
ACKNOWLEDGMENT
The CMM Department of Energy National User Center for
Electron Beam Microcharacterization, University of Illinois at
Urbana-Champaign, provided access to the SEM used in this
paper.
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Kuan-Lun Chu received the B.S. degree in physics
from National Taiwan University, Taipei, Taiwan,
in 1994, and the M. Eng. degree in electrical and
computer engineering from Cornell University,
Ithaca, NY, in 2001.
He is currently pursuing the Ph.D. degree in elec-
trical and computer engineering at the University of
Illinois, Urbana-Champaign. His research area is mi-
croelectromechanical systems for micropower gener-
ation
Scott Gold received the B.S. degree in chemical engi-
neering from the University of Kentucky, Lexington,
the M.S. degree from the Georgia Institute of Tech-
nology, Atlanta, and the Ph.D. degree from Arizona
State University, Tempe, in 2002.
He followed with a postdoctoral research position
at the Univesity of Illinois, Urbana-Champaign.
He joined the faculty at Louisiana Tech University,
Ruston, in 2004. He works in micromechincal
systems and micropower generation.
Vaidyanathan (Ravi) Subramanian received the
Ph.D. degree in chemical engineering from the
University of Notre Dame, South Bend, IN, in 2004.
He is currently a visiting research Assistant
Professor with Prof. Richard Masel at the University
of Illinois, Urbana-Champaign, in the Chemical
and Biomolecular Engineering Department. His
research area is synthesis and applications of semi-
conductor-metal nanocomposites to alternate energy
systems, sensors, and environmental systems.
CHU et al.: NANOPOROUS SILICON MEMBRANE ELECTRODE ASSEMBLY 677

Chang Lu received the B.S. degree in chemistry
from Peking University, Beijing, China, in 1998, and
the M.S. and Ph.D. degrees in chemical engineering
from the University of Illinois, Urbana-Champaign,
in 2001 and 2002, respectively.
He followed with a post doctorate at the
Nanobiotechnology Center at Cornell University,
Ithaca, NY. He is now an Assistant Professor at
Purdue University, West Lafayette, IN. His research
group focuses on the use ofmicro/nano scale devices
and materials in the study of biological systems and
for harnessing biological energy. More specifically, part of the effort is directed
toward development of micro/nano devices for biological sample treatment and
processing.
Richard I. Masel received the M.S. degree in chem-
ical engineering in 1973 from Drexel University,
Philadelphia, PA, in 1973.
He joined the University of Illinois, Urbana-Cham-
paign, in 1978. He is now Professor of Chemical and
Biomolecular Engineering and Electrical and Com-
puter Engineering. Masel has worked on kinetics and
catalysis, and more recently fuel cells, microchem-
ical systems, and MEMS. He helped found Tekion,
a developer of fuel cells for portable electronics, in
2003. He served for three years as Chief Technical
Officer of Tekion before stepping down to the position of Chief Technical Ad-
visor. Recently, he and Mark Shannon founded Cbana Laboratories, a developer
of microfluidic products.

Mark A. Shannon received the B.S. and Ph.D. de-

grees in mechanical engineering from the University
of California, Berkeley, in 1989 and 1993, respec-
tively.
He joined the faculty of the University of Illinois,
Urbana-Champaign, in 1994. He is Willett Professor
of Mechanical and Industrial Engineering, Electrical
and Computer Engineering, Bioengineering, and
Director of the Center of Advanced Materials for
the Purification of Water with Systems. His research
is in microfabrication, micro electrical mechanical
systems, micro/nanofluidics, and BioMEMS. Recently, he and Richard Masel
founded Cbana Laboratories, a developer of microfluidic products.

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