Nanowires Recent work has focused on the fabrication of metallic
nanowire patterns within AAO membranes on top of
DOI: 10.1002/smll.200700724
Nanowire-Decorated Microscale
Metallic Electrodes**
Alexandru Vlad, Maria Matefi-Tempfli, Vlad A. Antohe,
Sebastien Faniel, Nicolas Reckinger, Benoit Olbrechts,
Andre Crahay, Vincent Bayot, Luc Piraux, Sorin Melinte,*
and Stefan Matefi-Tempfli*
One of the challenging aspects of science and technology on a
nanometer-scale is the precise three-dimensional control of
nano-objects. Scanning probe microscopy manipulation,
magnetic- or electric-field alignment and lithography-based
techniques are only a few of the techniques that have been
reported so far.[1] Nevertheless, most of these techniques are
still being developed and their integration for device
fabrication represents a real challenge for the scientific
community. Within this context, nanowires and nanotubes
are of great interest because they lie between the macroscopic
and atomic scales. The ability to fabricate and manipulate such
objects in a reliable manner on a large scale will foster their use
in electronic, photonic, and sensing applications.[2] Template-
based methods have been successfully used for nanowire
fabrication as they allow the realization of complex organic/
inorganic nanostructures.[3] To date, nanoporous anodic
alumina oxide (AAO) made by the electrochemical oxidation
of aluminum has been extensively used because it provides a
good platform for the development of various nanostructures.
This interest originates from the fact that AAO membranes,
having a high density of nanopores (up to 1012 cm
2), are easily
produced over large areas with variable thicknesses.[4] More-
over, a good chemical and mechanical stability combined with
interesting electrical properties make AAO membranes good
candidates for nanowire fabrication. However, the use of such
nanostructures as passive or active components in emerging
electronic devices requires smartly engineered arrays of
nanowires with well defined position and pitch.
[] A. Vlad, Dr. S. Faniel, N. Reckinger, B. Olbrechts, A. Crahay,
Prof. V. Bayot, Dr. S. Melinte
Laboratoire de Microelectronique (DICE)
Universite catholique de Louvain (UCL)
Place du Levant 3, Louvain-la-Neuve, B-1348 (Belgium)
Fax: (32) 10 47 2598
E-mail: sorin.melinte@uclouvain.be
M. Matefi-Tempfli, V. A. Antohe, Prof. L. Piraux,
Dr. S. Matefi-Tempfli
Physico-chimie et physique des materiaux
Universite catholique de Louvain (UCL)
Place Croix du Sud 1, Louvain-la-Neuve, B-1348 (Belgium)
Fax: (32) 10 47 3452
E-mail: matefi@uclouvain.be
[] This work was partially supported by the FNRS, the NANOMOL
project (Actions de Recherches ConcerteesCommunaute
Francaise de Belgique), and by the Interuniversity Attraction Pole
Program (P6/42) - Belgian State - Belgian Science Policy. We
gratefully acknowledge financial support for this study from the
Government of the Walloon Region (NANOTIC project).
small 2008, 4, No. 5, 557560 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
continuous conducting substrates.[5] Lithography-based
approaches defined the shape of the patterns, while the
anodization conditions controlled the aspect ratio (height to
diameter ratio) and the density of the nanowires. The resulting
structures are of paramount importance for photonics,[6] field
and light emission emitters,[7] as well as surface treatments.[8]
However, the drawback of all these techniques is that the
fabricated structures are lying on a conductive substrate
therefore prohibiting any direct integration into a real
electronic device. This could have been achieved by further
processing such as additional patterning and selective etching
of the alumina membrane and of the underlying conductive
film. Still, this has not yet been realized and this approach
would increase the complexity of the fabrication process.
Herein we report on a versatile approach for generating
electrically separated nanowire patterns in only one patterning
step. To extend further the process, we confine spatially
the growth. The influence of the substrate nature upon the
fabricated structures is presented and discussed. The pre-
sented work offers the potential for the integration of
the alumina embedded nanowires into vertical electronics.
The most representative device being the realization of
crossbar latches comprising single nanowires at each crossing
point (Figure 1, step 5). As has been highlighted by Hewlett
Packard researchers, this technology could possibly replace
conventional transistor strategy.[9]
The fabrication protocol is based on the realization of
nanowire patterns using supported nanoporous alumina
templates (SNATs) prepared on top of lithographically
defined metallic microelectrodes. Complete anodization of
the aluminum permits electroplating only on top of the
metallic electrodes, leading to the nanowire patterns having
the same shape as the underlying metallic tracks (referred to
here as the 1st generation nanowire pattern). Further, confined
nanowire structures are created on top of the metallic
electrodes by surface texturing (hereafter called the 2nd
generation nanowire pattern).
Figure 1 summarizes the process flow for the fabrication of
both types of nanowire pattern. After the deposition of the
aluminum layer the sample is anodized in order to obtain the
SNAT. At this stage, electroplating and matrix release will
yield 1st generation nanowire patterns. In the case of confined
growth, the plasma-enhanced chemical-vapor-deposited sili-
con nitride film is patterned using electron-beam lithography
and reactive-ion etching to provide openings for the selective
electrochemical growth. After the electrodeposition, the SiN
and the alumina template are removed to reveal 2nd genera-
tion, freestanding nanowire structures. For comparison,
reference samples were prepared following the same proce-
dures with the exception that a continuous conductive layer
was used instead of microelectrodes.
Examples of architectures fabricated on top of lift-off-
patterned microelectrodes are presented in Figure 2. Analysis
of pristine, nonpatterned substrates samples (Figure 2a)
reveals a high degree of uniformity of the grown structures.
The few detectable voids are mostly due to the coalescence of
the nanowires tip after the dissolution of the alumina. The
557
 communications
same characteristics can be ascribed to
the confined grown nanostructures (Fig-
ure 2c). A barely detectable difference in
the number of nanowires inside each
fabricated nanobunch is observed, in
accordance with the behavior displayed
by the pristine samples. A slightly
different situation occurs in the case of
patterned substrates (Figure 2b and 2d).
An increase in the number of void-type
defects is detected on the 1st generation
patterns in comparison with the non-
patterned samples (Figure 2a). The
absence of parasitic nanowires outside
the microelectrodes areas is noticeable.
The nanowire coverage varies from 65 to
85 percent of the area of the metallic
pads. The above-mentioned defects will
affect the quality of the confined nano-
wire electrodeposition (2nd generation
patterns), leading to small irregularities
in the structures grown (Figure 2d).
The variation in the fabricated struc-
tures between the patterned and non-
patterned substrates can be interpreted
Figure 1. Fabrication flow for the selective electrochemical growth of nanowire patterns on in terms of different behavior during
top of gold tracks (step 1 through 4). Step 5 is a schematic representation of a desired device. anodization (Figure 3). The high noise
The nanowires are embedded in alumina and are connected on both sides by an array of level and the modified shape of the
electrically isolated metallic strips forming a 3  3 crossbar circuit. a) top view of the alumina anodization curve for ordinary lift-off-
surface (scale bar is 500 nm); b) scanning electron microscopy (SEM) image of Ni nanowires
patterned samples are direct evidence
fabricated on metallic electrodes (scale bar is 2 mm).
for a disturbed anodization mechanism.
The anodic oxidation is altered by the
surface and bulk imperfections present in
the aluminum layer.[10] They originate from typical lift-off
problems (retention, ears, and redeposition) that increase the
surface roughness of the aluminum.[11]
Improved anodization conditions can be achieved using
defect-free patterned microelectrodes (red curves in Figure 3).
Two approaches have been successfully used: wet etching
definition and rigorous cleaning of lift-off-patterned metallic
strips. There are still some minor Y-type defects present
only at the edges of the microelectrodes (right panels in
Figure 3). Their nature is explained by the nonparallel pore
initiation caused by topographic profile. The electrodeposition
curves are smooth and alike, therefore supporting the
supposition that the critical fabrication step is the anodic
aluminum oxidation. The improved quality of fabricated
nanowire patterns is clearly demonstrated by the SEM
imaging. Figure 4 presents cross-section snapshots acquired
at the different stages of the processing. A uniform growth of
nanowires inside the alumina template is observed without any
significant height variation. Moreover, no parasitic wires are
found outside the microelectrodes area, reinforcing our
finding that the electroplating nucleates only on top of the
metallic strips without any additional patterning steps. After
the alumina removal, uniformly distributed close-packed
Figure 2. SEM images depicting the 4 types of the fabricated Ni
nanowire (diameter 80 nm, length 1.2 mm) structures: a) homogeneous nanowire patterns are found on the substrate (more than
and c) confined growth of nanowires on nonpatterned substrates. b) 1st 95% coverage) demonstrating the overall good nucleation and
and d) 2nd generation nanowire patterns. Scale bars are 2 mm. filling of the pores.

558 www.small-journal.com 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim small 2008, 4, No. 5, 557560

Figure 3. Left: Typical anodization curves of 1-mm-thick aluminum films deposited on
nonpatterned substrates (black), ordinary patterned substrates (green) and defect-
free patterned samples (red). The anodization conditions are identical in both cases.
Inset: Corresponding Ni electrodeposition curves. Right: SEM images of the
Y-branched defects after the anodic aluminum oxidation and the electroplating. Scale
bars are 1 mm.
Figure 4. Sequential SEM imaging of the fabrication steps (left:
enlarged view, right: one microelectrode close-up). Top: SNAT covering
the metallic tracks; middle: partial electroplating; bottom: free standing
nanowires after the removal of the alumina. Scale bars are 10 mm (left)
and 2 mm (right).
In conclusion, we have presented a versatile method for the
fabrication of ordered arrays of localized nanowires on top of
electrically disconnected micrometer-scale metallic electrodes.
By combining the anodic oxidation of aluminum on different
types of substrates and selective electrochemical growth,
complex nanoarchitectures have been realized. The selective
growth of nanowires on top of the microelectrodes stems from
small 2008, 4, No. 5, 557560 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
the fact that the electroplating takes place only
on electrically conducting areas. Thus, 1st and 2nd
generation nanowire patterns fabrication relies
either on simple electrochemical growth or on
the employment of a patterned mask deposited
on top of the SNAT. The presented work
represents one step further towards the integra-
tion of the supported nanoporous alumina into
large-scale micro- and nanoprocessing. The
nanowires-decorated metallic electrodes are of
great interest for the realization of crossbar
circuits for high-density vertical electronics.[12]
The use of a nanoporous template as the
precursor for the nanowire fabrication offers
the possibility to integrate a wider range of
nanometer-scale objects than with classical
processing methods. Moreover, because of their
extremely specific surface, these structures can
be very interesting for sensing applications as the
fabrication procedure allows both precise posi-
tioning and device integration, while the electro-
deposition yields a high degree of chemical
identity of the transducer.[13]
Experimental Section
First, a 100-nm-thick silicon oxide was grown on [100] silicon
wafers. Next, the samples were spin-coated with 1.5-mm-thick
image-reversal photoresist (AZ 5214E, MicroChemicals GmbH). An
i-line UV source was employed for exposure through a laser
generated photolithography mask (Photronics Inc.). After devel-
opment of the resist, a Ti (10 nm) and Au (50 nm) bilayer was
deposited using electron-beam evaporation, followed by lift-off in
acetone. The cleaning and the defect removal were performed by
prolonged ultrasonication in hot acetone in a cleanroom environ-
ment. The samples were not allowed to dry during all these steps
to avoid the irreversible deposition of the metallic dust on the
wafer. The etch-patterned samples were prepared as follows. The
Ti/Au stack was electron-beam evaporated on the oxidized wafers.
The same UV exposure procedure with a positive-tone photoresist
(AZ 6612, MicroChemicals GmbH) produces an inversed image of
the developed photoresist. The Au film was etched away in aqua
regia solution. After the photoresist removal, the wafers were
shortly dipped in a freshly prepared piranha etch solution to
remove the underlying Ti layer. No significant difference in
anodization was found between the etched and lift-off deconta-
minated patterned electrodes. Yet, the later microstructure has
the disadvantage of being less reproducible as the prolonged
ultrasonication may destroy the metallic strips.
Anodic oxidation of the 1000-nm-thick Al layer was performed
in H2C2O4 (0.3 M) at 60 V using a two-electrode cell. The electro-
lyte and the substrate were maintained at 2 8C during the
anodization process. The pores are enlarged in an orthopho-
sphoric acid solution (0.5 M) at 30 8C (typically 45 min for a pore
diameter of 90 nm).
After the anodization, the samples were cleaned in hot
acetone, rinsed with isopropanol and dried in a N2 stream. The
plasma enhanced chemical vapor deposition of the SiN layer
www.small-journal.com 559
 communications
(100-nm-thick film) was followed by the coating of the samples
with a 200-nm-thick film of positive electron-beam resist. After
electron-beam lithography, the pattern was transferred into the
SiN layer by reactive-ion etching using SF6.
The electrodeposition of the nanowires within the exposed
areas was carried out using an EG&G PAR 263 potentiostat
(Princeton Applied Research) in a conventional three-electrode cell [4]
with a Pt counter electrode and Ag/AgCl as reference electrode. In
order to ensure a homogenous growth, the pulse plating method
was used to deposit the Ni nanowires from a solution containing
NiSO4 (0.5 M) and H3BO3 (0.5 M) at room temperature.
Keywords:
alumina . electrodeposition . microstructures . [5]
nanolithography . nanowires
[1] a) D. M. Eigler, E. K. Schweizer, Nature 1990, 344, 524526; b) A. I.
Yanson, G. Rubio Bollinger, H. E. van den Brom, N. Agrat, J. M. van
Ruitenbeek, Nature 1998, 395, 783785; c) M. Tanase, D. M.
Silevitch, C. L. Chien, D. H. Reich, Appl. Phys. Lett. 2003, 93, 7616
7618; d) A. K. Bentley, J. S. Trethewey, A. B. Ellis, W. C. Crone, Nano
Lett. 2004, 4, 487490; e) P. A. Smith, C. D. Nordquist, T. N. [6]
Jackson, T. S. Mayer, B. R. Martin, J. Mbindyo, T. E. Mallouk, Appl.
Phys. Lett. 2000, 77, 13991401; f) A. Bachtold, P. Hadley, T.
Nakanashi, C. Dekker, Science 2001, 294, 13171320; g) L. Vila, L.
Piraux, J. M. George, G. Faini, Appl. Phys. Lett. 2002, 80, 3805 [7]
3807; h) M. E. Toimil Molares, E. M. Hohberger, Ch. Schaeflein,
R. H. Blick, R. Neymann, C. Trautman, Appl. Phys. Lett. 2003, 82,
21392141. [8]
[2] a) S. J. Hurst, E. K. Payne, L. Qin, C. A. Mirkin, Angew. Chem. 2006,
118, 27382759. Angew. Chem. Int. Ed. 2006, 45, 26722692; [9]
b) M. S. Dresselhaus, Y. M. Lin, O. Rabin, A. Jorio, A. G. Souza Filho,
M. A. Pimenta, R. Saito, Ge. G. Samsonidze, G. Dresselhaus, Mater. [10]
Sci. Eng. C 2003, 23, 129140; c) J. E. Green, J. W. Choi, A. Boukai,
Y. Bunimovich, E. Johnston-Halperin, E. Delonno, Y. Luo, B. A. [11]
Scheriff, Y. S. Shin, H.-R. Tseng, J. F. Stoddart, J. R. Heath, Nature [12]
2007, 445, 414417; d) Y. Cui, C. M. Lieber, Science 2001, 291,
851853.
[3] a) J. C. Hulteen, C. R. Martin, J. Mater. Chem. 1997, 7, 10751087; [13]
b) Z. Zhang, J. Y. Ying, M. S. Dresselhaus, J. Mater. Res. 1998, 13,
17451748; c) T. Thurn-Albrecht, J. Schotter, G. A. Kastle, N.
Emley, T. Shibauchi, L. Krusin-Elbaum, K. Guarini, C. T. Black,
M. T. Tuominen, T. P. Russel, Science 2000, 290, 21262129;
d) L. Piraux, A. Encinas, L. Vila, S. Matefi-Tempfli, M. Matefi-
Tempfli, M. Darques, F. Elhoussine, S. Michotte, J. Nanosci. Nano-
technol. 2005, 5, 372389; e) M. Lahav, E. A. Weiss, Q. Xu, G. M.
560 www.small-journal.com 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Whitesides, Nano Lett. 2006, 6, 21662171; f) M. Steinhart, S.
Zimmermann, P. Goring, A. K. Schaper, U. Gosele, C. Weder, J. H.
Wendorff, Nano Lett. 2005, 5, 429434; g) N. I. Kovtyukhova, T. E.
Malouk, Adv. Mater. 2005, 17, 187192; h) A. Johansson, E.
Widenkvist, J. Lu, M. Boman, U. Jansson, Nano Lett. 2005, 5,
16031606; i) R. Sanz, M. Hernandez-Velez, K. R. Pirota, J. L.
Baldonedo, M. Vazquez, Small 2007, 3, 434437.
a) H. Masuda, K. Fukuda, Science 1995, 268, 14661468; b) W.
Lee, R. Ji, U. Gosele, K. Nielsch, Nat. Mater. 2006, 5, 741747; c) I.
Mikulskas, S. Juodkazis, R. Tomasiunas, J. G. Dumas, Adv. Mater.
2001, 13, 15741577;d) W. Lee, R. Ji, C. A. Ross, U. Gosele, K.
Nielsh, Small 2006, 2, 978982; e) J. Mallet, K. Yu-Zhang, S.
Matefi-Tempfli, M. Matefi-Tempfli, L. Piraux, J. Phys. D: Appl. Phys.
2005, 38, 909914; f) Y. Matsui, K. Nishio, H. Masuda, Small
2006, 2, 522525.
a) A.-P. Li, F. Muller, A. Birner, K. Nielsh, U. Gosele, Adv. Mater.
1999, 11, 483487; b) O. Rabin, P. R. Herz, Y.-M. Lin, A. I.
Akinwande, S. B. Cronin, M. S. Dresselhaus, Adv. Funct. Mater.
2003, 13, 631638;c) F. Li, M. Zhu, C. Liu, W. L. Zhou, J. B. Wiley, J.
Am. Chem. Soc. 2006, 128, 1334213343;d) A. Vlad, M. Matefi-
Tempfli, S. Faniel, V. Bayot, S. Melinte, L. Piraux, S. Matefi-Tempfli,
Nanotechnology 2006, 17, 48734877; e) B. Wolfrum, Y. Mour-
zina, D. Mayer, D. Schwaab, A. Offenhausser, Small 2006, 2,
12561260.
a) J.-Y. Ye, V. Mizeikis, Y. Xu, S. Matsuo, H. Misawa, Opt. Commun.
2002, 211, 205213; b) T. Martensson, P. Carlberg, M. Borgstrom,
L. Montelius, W. Seifert, L. Samuelson, Nano Lett. 2004, 4, 699
702.
L. Vila, P. Vincent, L. Dauginet-De Pra, G. Pirio, E. Minoux, L.
Gangloff, S. Demoustier-Champagne, N. Sarazin, E. Ferain, R.
Legras, L. Piraux, P. Legagneux, Nano Lett. 2004, 4, 521524.
S. Petronis, J. Gold, B. Kasemo, J. Micromach. Microeng. 2003, 13,
900913.
P. J. Kuekes, D. R. Stewart, R. S. Williams, J. App. Phys. 2005, 97,
034301.
F. Matsumoto, M. Harada, K. Nishio, H. Masuda, Adv. Mater. 2005,
17, 16091612.
J. W. Penney, US Patent 1987, 4 687 541.
M. Umemoto, K. Tanida, Y. Remoto, M. Hocino, K. Kojima, Y. Shirai,
K. Takahashi, Proc. 54th Electronic Components and Technology
Conference 2004, 1, 616623.
a) R. Gasparac, B. J. Taft, M. A. Lapierre-Devlin, A. D. Lazareck, J. M.
Xu, S. O. Kelley, J. Am. Chem. Soc. 2004, 126, 1227012271; b) M.
Yun, N. V. Myung, R. P. Vasquez, C. Lee, E. Menke, R. M. Pender,
Nano Lett. 2004, 4, 419422.
Received: August 20, 2007
Revised: February 12, 2008
Published online: April 4, 2008
small 2008, 4, No. 5, 557560