Microelectronic Engineering 66 (2003) 166170

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Fabrication and characterization of anodic aluminum oxide

template
Xin Wang*, Gao-Rong Han
Department of Materials Science and Engineering, State Key Laboratory of Silicon Materials, Zhejiang University,
Hangzhou, Zhejiang 310027, China

Abstract
In this paper, anodic aluminum oxide (AAO) templates were fabricated using a two-step oxidization method,
pore-widening was then fulfilled in 5 wt% phosphoric acid at 37 8C. The AAO template prepared under 40 V
constant potential presents the optimum ordering. The pore diameter and spacing are proportional to the forming
voltage, which is due to the alternative migration velocity of reactive ions under electric field according to the
growthdissolution model. Further pore adjustment depends on the time of pore-widening in phosphoric acid.
The characterization of the AAO template was measured by atomic force microscopy (AFM) and X-ray
diffraction (XRD).
2003 Elsevier Science B.V. All rights reserved.
Keywords: AAO template; Pore-widening time; AFM

1. Introduction
Since the successful growth of carbon nanotube, great interest has been focused on one-dimensional
materials, including nanotube and nanowire, because of their unique structure and properties as well
as potential applications in electronics, mechanics and optical devices [1,2]. To actualize most of the
proposed applications, it is quite important to obtain highly ordered nanostructure arrays. While there
are technological as well as economical limitations in lithography for ultra large scale integrated
fabrication in the forthcoming stage of sub-100 nm scale, much effort has been focused on
nanostructure formation by self-organizing methods. Among them, the anodic aluminum oxide (AAO)
templates have received considerably attention in synthetic nanostructure material due to their
particular characters such as controllable pore diameter and periodicity, extremely narrow distribution
of pore size, and the pore has ideal cylindrical shape [38]. This offers a promising route to
* Corresponding author. Tel.: 1 86-571-8795-2341; fax: 1 86-571-8795-2341.
E-mail address: wxzju@zju.edu.cn (X. Wang).
0167-9317 / 03 / $ see front matter 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016 / S0167-9317(03)00042-X

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167

synthesize a large-area, ordered nanostructure with high aspect ratio, which is quite difficult to form
by conventional lithographic process. Yet the arrangement of the pores is quite disordered using the
traditional anodization method. Masuda et al. [9] advanced two-step anodization process, leading to
perfect hexagonal pore structure for certain sets of parameters. Since the ordering of the pore
arrangement of AAO controls the regularity of further nanostructure fabricated using AAO as host
material, the influence of experimental parameters on the structure of AAO is focused on in this paper.

2. Experimental
The AAO templates were fabricated by a two-step anodization process. Specimens of 99.999%
aluminium foils annealed at 500 8C for 5 h in vacuum were electrochemically polished in a mixture of
concentrated sulfuric and phosphoric acids. After electrochemically polishing, the specimens were
anodized at 3050 V in 0.3 M oxalic acid aqueous solution at room temperature. Then the anodic
oxide layer, part of which was disorderly, was removed in a mixture of phosphoric acid and chromic
acid. After removal of the anodic oxide layer, the textured Al plate was anodized again under
conditions identical to those for the first anodizing step. Then the Al layer of the specimen was
removed in a saturated HgCl 2 solution. The bottom part of the membrane was removed by exposure
to phosphoric acid at 37 8C. Some as-synthesized AAO template is further annealed at 800 8C for 5 h
in atmosphere. Three representative samples were selected as shown in Table 1. The AAO templates
were characterized by atomic force microscope (AFM) and X-ray diffraction (XRD).

3. Results and discussion

Curve a and b in Fig. 1 correspond to the XRD spectra of sample A without and with annealing. In
curve a, the broad peak around 278 indicates that the as-synthesized AAO is amorphous, while in
curve b, the reflection peaks of (311), (222), (400), (511) and (440) corresponding to the g-Al 2 O 3
phase appear, which implies that the AAO transforms from amorphous to crystalline after anneals in
high temperature.
Fig. 2a and b are the three-dimensional AFM images of sample A and B, respectively. The results
show distinctly that an ordered honeycomb structure with uniformity in pore-diameter and spacing can
be fabricated with this method. In Fig. 2a, the pore diameter is 20 nm and pore spacing is 80 nm for
AAO prepared under 40 V, while AAO prepared under 50 V has pore size of 35 nm in diameter and
spacing of 110 nm as shown in Fig. 2b. It illustrates that the pore diameter and spacing increase with
Table 1
Experimental parameter of samples prepared
Sample

Voltage
(V)

Temperature
(8C)

Pore-widening
time (min)

A
B
C

40
50
40

15
15
15

30
30
45

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X. Wang, G.-R. Han / Microelectronic Engineering 66 (2003) 166170

Fig. 1. XRD spectra of sample A (a) without and (b) with annealing.

increasing voltage. In addition, sample A prepared under lower voltage is more regular than sample B.
According to the growth model proposed by Xu et al. [10], pores are first formed at certain
micro-rough region where the current density is concentrated on after the formation of steady barrier
layer and then the pores grow perpendicular to surface with an equilibrium of field-enhanced oxide

Fig. 2. AFM images of (a) AAO prepared under 40 V (1800 nm 3 1800 nm), and (b) AAO prepared under 50 V (1800
nm 3 1800 nm).

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Fig. 3. (a) AFM image of AAO after pore-widening for 45 min (1500 nm 3 1500 nm), and (b) curve correlating mean pore
diameter with widening time.

dissolution at the oxide electrolyte interface and oxide growth at the metal / oxide interface, and the
horizontal grow is performed simultaneously. In this process, the repulsive interaction between the
pore, which is associated with the expansion of the aluminum during anodization impulses the
structural adjustment to form honeycomb like pore arrays. With the enhancement of anodizing
voltage, the longitudinal growth of the pores increases due to the lager migration velocity of the
reactive cation and anion ions, which can be confirmed by the thickening of the AAO (data not
shown) and the horizontal growth also increases leading to the enlargement of the pore diameter and
spacing. At the same time, the adjustment velocity among the pores cannot keep up with the growth
velocity of AAO and the quality of the ordering of this structure might decrease.
Although AAO prepared after two-step anodization possesses controllable pore diameter and
periodicity, further pore adjustment can be actualized by exposure to phosphoric acid, what is called
pore-widening. The AFM image of sample C prepared after pore-widening for 45 min is shown in
Fig. 3a. In compare with sample A prepared after pore-widening for 30 min, the pore diameter
increases to 40 nm, while the pore spacing almost keeps unchanged. A curve correlating mean pore
diameter with widening time described in Fig. 3b illustrates that the mean pore diameter is
monotonously increased with increasing the pore-widening time. The increase of pore diameter after
immersing into phosphoric acid might be due to the etching effect of phosphoric acid that results in
the thinning of the outer and inner surface of AAO. This provides a convenient route to prepare AAO
template of any desired pore diameter in the range shown in the Fig. 3. Then, any diameter nanowire
can be synthesized in its pore.

4. Conclusions
We have successfully prepared highly oriented porous structure with uniform and nearly parallel
pores using two-step anodizing method. XRD results show that AAO transforms from amorphous to

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crystalline after annealing in high temperature. The AAO template prepared under 40 V constant
potential presents the optimum ordering. The pore diameter depends on both anodizing voltage and
time of pore-widening in phosphoric acid. The relation between the ordering of the pore arrays and
anodizing voltage is explained by a growthdissolution model.

Acknowledgements
The work is supported by the Talents Across the Century of the Education Ministry of China and
NSFE (69890230).

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