COMMUNICATION

DOI: 10.1002/adma.200701284

Novel Structure of AAO Film Fabricated by Constant Current

Anodization**
By Shiyong Zhao,* Karen Chan, Arthur Yelon, and Teodor Veres*

Since Masuda and Fukuda’s study of self-ordered porous determinant of the interpore distance, and the pH value of
alumina membranes by a two-step replicating process,[1] anod- the electrolyte, which provides the primary control of the pore
ized aluminum oxide (AAO) membranes have became one of radius, are adjusted so that the membrane porosity is 10 %.
the most common nano-templates for the preparation of Ono et al.[14] reported that high current density or high elec-
nanowires,[2–5] nanotubes,[6] ordered arrays of nanoparticles,[7] tric-field strength is the key factor for the self-ordering of
nanorings and nanocones.[8] These AAO films are also widely AAO films. Recently, Chu et al.[15,16] and Li et al.[17] have re-
used as filters,[9] and as 2D photonic crystals.[10] ported the fabrication of ordered AAO films with various in-
The usual electrochemical method for producing the AAO terpore distances by using high fields and H2SO4 or H3PO4–
film is the anodization of high purity Al plates at constant H2O–C2H5OH solutions. Lee et al.[18] have recently proposed
voltage, which provides only limited control over the pore the so-called ‘hard-anodization’ approach[19–22] for fast fabri-
spacing using different anodization conditions:[11] 66 nm cation of AAO films, on which potentials of 100–150 V are ap-
(0.3 M H2SO4, 25 V), 100 nm (0.3 M oxalic acid, 40 V), and plied in oxalic acid solution. To suppress breakdown effects
500 nm (0.1 M H3PO4, 195 V) and leads to a hexagonal pore and to permit uniform oxide film growth, an oxide layer
array. Attempts have been made to create nano-porous AAO (thickness > 400 nm) was formed on the surface of the alumi-
membranes with symmetries other than hexagonal pack- num substrate before the hard-anodization was carried out.
ing.[12,13] Krishnan et al.[12] prepared AAO alumina mem- Mosaic nanowire arrays fabricated with AAO templates
branes with a square arrangement of nanopores on Si sub- would be very useful for functional electrodes, sensors, model
strates by using a square array of indentations. These were catalysts and optical devices. For example, Masuda et al.[23]
made by patterning and chemical wet etching of sites for have prepared ordered mosaic nanocomposites of Au and Ni
forced annodisation. Sun et al.[13] obtained an AAO mem- in AAO film by pretexturing the aluminum. In this paper, we
brane with a square lattice of square nanopores using an an- present a constant current method for producing AAO mem-
odized Aluminum film deposited on a photoresist-grating pat- brane, in which high current density was applied over the en-
tern developed on a silica substrate. Both approaches use tire anodization time in order to prepare an ordered AAO
indirect methods (mechanical indentation or lithography) in film. This process leads to the formation of a novel AAO
order to pre-process the substrates prior to anodization. membrane with a six-membered ring symmetry co-existing
Nielsch et al.[11] proposed a method for the fabrication of with the usual hexagonal structure. The pore sizes of this
self-ordered porous alumina with the interpore distance cus- structure can be tailored by changing the processing condi-
tomized using a 10 % porosity rule. They reported that long tions. These new pore structures have great potential applica-
range ordering is possible if the applied potential, the main tions in nanomaterials fabrication, particular in the mosaic
nanowire arrays.
Usually only low voltage (and low current) can be used for
– stable anodization in H2SO4 solution because of the occur-
[*] Dr. S. Zhao, Dr. T. Veres, K. Chan rence of breakdown or ‘burning‘ of the AAO film due to cor-
Industrial Materials Institute, National Research Council Canada
75 de Mortagne Blvd, Boucherville, QC, J4B 6Y4 (Canada) rosive acid attack under a high electric field. Chu et al.[15]
E-mail: [email protected]; found that the critical high anodizing potential, i.e., the break
[email protected] down or burning potential of AAO films in the electrolyte sys-
Dr. S. Zhao, Prof. A. Yelon tem adopted, increased with the ageing of the solution after a
École Polytechnique de Montréal
Département de Genie Physique et Regroupement Quebecois sur long period of anodization. By adjusting the state of H2SO4
les Materiaux de Pointe (RQMP) solution by ageing the solution over a long period of anodiza-
CP 6079, Succursale Centre-ville, Montréal, Québec, H3C 3A7 tion (10–20 A h l–1), they obtained uniform AAO films in
(Canada)
H2SO4 solution under a high electric field of 40–70 V and cur-
K. Chan
Simon Fraser University rent density of 1600–2000 A m–2. Considering that the ageing
8888 University Drive Burnaby, B.C. V5A 1S6 (Canada) of H2SO4 solution results in the replacement of H+ by Al3+,
[**] The authors thank Helene Roberge, Bo Cui and Francois Norman- we have used a solution of H2SO4 + Al2-(SO4)3 instead. We
din for their assistance with the sample preparation and analysis. have used a constant current method with current density of
This research has been supported by the National Sciences and En-
gineering Research Council of Canada (NSERC) and the National 160 mA cm–2. The constant current promises the constant
Research Council of Canada (NRC). growth rate of AAO film, in contrast with that reported by

3004 © 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Mater. 2007, 19, 3004–3007
 COMMUNICATION
Chu et al. In their work, the potential was kept
constant during anodization while the current var-
ied. Figure 1 shows the voltage-time curves of our
constant current anodization. In the 0.8 M
H2SO4 + 0.1 M Al2(SO4)3 solution, the voltage first
increases gradually from 24 V to a maximum of
90 V at 27 min. Then, it decreases to 40 V. How-
ever, if the anodization is performed without
Al2(SO4)3, the anodic dissolution of Al in the 0.8 M
H2SO4 solution is very fast. Even at a current of
160 mA cm–2, the voltage stays at about 3 V. In
that case, no ordered AAO film can form on the
aluminum surface. Figure 2a is a bottom-view
SEM image of an AAO film anodized in a solution
of H2SO4 + Al2(SO4)3 for 30 min at 1 °C. The re-
maining aluminum substrate was removed in a
mixed solution of HCl/CuCl2 for 20 min. From Fig-
ure 2a it may be seen that the pores are closed and
covered by hemispherical shaped caps, evenly dis-
tributed on the surface, in a hexagonal structure. Figure 2. SEM of AAO with novel structure. a) Bottom view just after removal of the
This indicates that anodization with a constant cur- Al substrate in a mixed solution of HCl/CuCl2 (immersion for 20 min), nanopores are
closed; b) small (15 nm diameter) pores arranged in six-membered ring are revealed
rent can be used to obtain ordered AAO tem- after a 40 min immersion; c) extending the immersion time to 60 min, the size of the
plates. This is consistent with the results of Chu et pores increases to 25 nm; d) after immersion in 5 % H3PO4, the usual hexagonal
al.[15] The interpore distance is 85 nm. However, structure of nanopores with 55 nm diameter and 85 nm inter-pore distance is re-
when the immersion time in HCl/CuCl2 was ex- vealed. The scale bar in the figures is 100 nm.
tended to 40 min, smaller pores (diameter of
15 nm) located at all junctions of three cell bound-
aries (triple points) were found (Fig. 2b). These pores are ar- Figure 3a is a sectional image of the AAO sample, confirm-
ranged as a six-membered ring structure with an interpore dis- ing that normal AAO nanopores (as shown by the arrows)
tance of 50 nm. This structure has never been reported in having an interpore distance of 85 nm are closed, while the
AAO nanoprous membranes. The size of the pores can be smaller pores (as shown by the open arrows) at the triple cell
controlled (increased) by increasing the immersion time
(Fig. 2c, immersing time 60 min, diameter of 25 nm). The
larger pores cannot be opened by immersion in the HCl/
CuCl2 solution. This can be done in H3PO4 solution. The
SEM image of an AAO film is shown in Figure 2d after im-
mersion in 5 % H3PO4 solution at 30 °C for 20 min. The entire
barrier layer has been removed and two networks of nano-
pores are revealed. We can observe that each of the large
pores (55 nm diameter) of the usual hexagonally packed net-
work is surrounded by six smaller pores, arranged in a six-
membered ring structure.

100 0.8M H2SO4+0.1MAl2(SO4)3

0.8M H2SO4
Voltage / V

50

Figure 3. a) Cross-sectional SEM image of the AAO sample after immer-

sion in a mixed solution of HCl/CuCl2 for 40 min. This reveals that the
0
six-membered ring structure pores are opened at the triple cell junction
0 10 20 30 (indicated by the open arrows) of the hexagonally packed normal nano-
Time / min pores (arrows) which are still closed. b) SEM image of the top surface of
an AAO film after immersion in 5 % H3PO4 for 15 min at 30 °C. The nor-
Figure 1. Voltaje-time curves during the constant current anodization of mal nanopores (40 nm diameter) are opened and circled by six small
Al with a current density of 160 mA cm–2. pores (15 nm diameter). The bars are 100 nm.

Adv. Mater. 2007, 19, 3004–3007 © 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.advmat.de 3005
COMMUNICATION

junction are already opened. The small pores belonging to the formation of the six-membered ring of small pores (shown in
six-membered ring structure are formed at the bottom surface Fig. 4Ba). Some voids or hydrated oxide should remain in the
as observed in Figure 2 but span over the whole thickness barrier layer of a small pore at a triple cell junction site. This
(50 lm) of the AAO film as confirmed by the AAO top sur- hydrated aluminum oxide is easily dissolved in aqueous HCl/
face SEM image shown in Figure 3b. CuCl2 solution; while the alumina barrier layer of the large
In the work of Choi et al.,[24] it was reported that the forma- pores is not. Thus, upon immersion in HCl/CuCl2 the small
tion of new pores in AAO templates can be guided over a pores opened and the six-membered ring of small pores ob-
large area by pre-patterning of the Al film by imprint lithogra- served, while large pores remained covered with the hemi-
phy. In preparing alumina nanotubes, Pu et al.[25] found that spherical barrier layer (Figs. 2b, c, 3a, and 4Bb). When the
after anodization with a high electric field (40 V in 15 % barrier layer of the large pores was removed by immersion in
H2SO4 solution), voids were often observed at the junction of H3PO4 solution, the hexagonal cell structure of large pores
the cell boundaries. Chu et al.[15] inferred that the aluminum was also revealed, with each large pore surrounded by six
oxide at the triple cell junction may not be as dense as the small pores as shown in Figures 2d and 4Bc.
other parts of the cell walls, due to the circularly distributed The novel structure, with high pore density described here,
expansion force (a repulsive force arising from volume expan- may be used in the preparation of nanomaterials for sensing
sion during film growth) from the centers of the alumina cells, applications such as nanostructured SERS (surface enhance
leading to preferential dissolution of the triple junction. Mei Ramen spectrum) and SPR (surface Plasmon spectrum) ac-
et al.[26] found that with high voltage anodization (40 V in tive surfaces for which the creation of ordered and closely
15 % H2SO4 solution), there is some hydrated aluminum ox- packed arrays of metal (Ag, Au) nanodots is desired. We have
ide (e.g., Al(OH)3 or AlOOH) in the alumina nanotube walls. developed an application of AAO films for the preparation of
In 1991, Ono et al.[27] had already found that the voids are ordered nanoring and nanocone arrays using the conical
only located at triple points in the AAO membrane and that openings of an AAO film as a mold.[8] Figure 5 shows the
the voids increase in size with increasing anodizing voltage. AFM image of an Ag film e-beam evaporated onto and subse-
Macdonald[28] proposed that the voids are produced by cation quently detached from the surface of an AAO film such as
vacancy condensation below regions in the barrier film (triple shown in Figure 2c. The nanopores are hexagonally ordered;
points) characterized by high cation vacancy diffusivity, due around every nanopore, there are six nanodots which have
to the high degree of lattice disorder. As the applied voltage the six-membered ring structure symmetry.
is made larger, vacancy condensation will occur more rapidly, In summary, we have prepared a novel symmetry six-mem-
thereby resulting in larger voids. bered ring structure of AAO film by constant current anod-
Based on these reports, the formation of the symmetric six- ization. The interpore distance is reduced from the usual
membered ring structure can be explained as follows: during 85 nm to 50 nm and this doubles the pore density. Ordered ar-
the constant current anodization process employing high cur- rays of nanodots with novel structure have been fabricated by
rent density or high voltage, voids are easily and rapidly this AAO template. The pore diameter can be easily con-
formed at the triple cell junction site (Fig. 4Aa). Many voids trolled by the HCl/CuCl2 immersion time and the solution
are formed successively at the same triple point (Fig. 4Ab). conditions. The investigations of six-membered ring structure
These merge into a small pore (Fig. 4Ac), thus leading to the

A a b c

60nm
a b c
B 0nm

Figure 4. Schematic illustration of formation of A) small pores at the tri-

ple cell junction site: a) Voids formed at the triple cell junction site,
b) many voids formed successively at the same triple junction, c) the
voids formed successively at the same triple point merge into a small
pore; B) novel six-membered ring structure of AAO: a) after anodization
and removal of the Al substrate the two networks of nanopores are
formed, but covered with hemispherical barrier layers; b) the barrier layer Figure 5. 3D AFM image of the surface of an Ag film e-beam evaporated
of the small pores is removed in a mixed solution of HCl/CuCl2, and the onto the surface of AAO film with symmetry structure of six-membered
six-membered ring is formed; c) the barrier layer of the large pores is re- rings then detached from the AAO film. The nanopores are hexagonally
moved in a solution of H3PO4, and all the pores are open-through. ordered, and the nanodots have a six-membered ring structure.

3006 www.advmat.de © 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Mater. 2007, 19, 3004–3007
 COMMUNICATION
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