Preparation and photoluminescence of alumina membranes with ordered

pore arrays
Y. Du, W. L. Cai, C. M. Mo, J. Chen, L. D. Zhang et al.

Citation: Appl. Phys. Lett. 74, 2951 (1999); doi: 10.1063/1.123976

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APPLIED PHYSICS LETTERS VOLUME 74, NUMBER 20 17 MAY 1999

Preparation and photoluminescence of alumina membranes

with ordered pore arrays
Y. Du, W. L. Cai,a) C. M. Mo, and J. Chen
Department of Materials Science and Engineering, University of Science and Technology of China,
Hefei 230026, People’s Republic of China
L. D. Zhang and X. G. Zhu
Institute of Solid State Physics, Academia Sinica, Hefei 230031, People’s Republic of China
~Received 18 November 1998; accepted for publication 18 March 1999!
Porous alumina membranes with ordered pore arrays were prepared electrochemically from Al
metal in C2H2O4 or H2SO4. Photoluminescence ~PL! measurements show that a blue PL band
occurs in the wavelength range of 400–600 nm. This band originates from singly ionized oxygen
vacancies (F 1 centers! in porous alumina membranes. Tentative reasons for the changes in intensity
and peak position of the PL band with increasing heat-treatment temperature are discussed.
© 1999 American Institute of Physics. @S0003-6951~99!03820-6#

Preparation of alumina membranes with ordered pore ar-
rays under anodic bias in various electrolytes has been car-
ried out for over 40 years.1 Porous alumina membranes are
used for fabrication of nanocomposites which present many
new properties.2–4 However, to the best of our knowledge,
the physical properties of the porous alumina itself have not
been investigated intensively. Study of the self-properties of
porous alumina is important to investigate the mechanisms
of new properties appearing in nanocomposites synthesized
using porous alumina as templates, because the self-
properties of the porous alumina certainly affect the proper-
ties of nanocomposites. Therefore, in this letter, alumina
membranes with ordered nanopore arrays were prepared
electrochemically and the photoluminescence ~PL! of porous
alumina membranes was investigated. Mechanisms of the
photoluminescence and characterization behaviors of the PL
band were discussed.
High-purity ~99.999%! aluminum foil was used as the
starting material. Before anodization the aluminum was de-
greased with acetone and then annealed at 500 °C for 4 h in
vacuum of about 1023 Pa. Porous alumina membranes were
prepared in a two-step anodizing process.4 The aluminum
foil was anodized in 0.3 M oxalic acid (C2H2O4) or 0.3 M
sulfuric acid (H2SO4) electrolyte. The anodizing voltage was
40 V for C2H2O4 and 27 V for H2SO4, respectively. The
temperature of the electrolyte was kept constant at 5 °C.
After the 10 h anodization, the specimens were immersed in
a mixture of 6 wt % H3PO4 and 1.8 wt % H2CrO4 at 60 °C
for 12 h to remove the alumina layers. Then, the aluminum
foil was anodized again for 5–10 h under the same anodiza-
tion condition as the first step. The thickness of the alumina
membranes was about 50–100 mm and aspect ratios ~ratios
of depth to diameter! of the pores of over 1000 were ob-
tained. At the bottom of the alumina membranes existed the
remaining aluminum layers. In some samples the remaining
aluminum layers of the porous alumina membranes were re-
moved in a saturated HgCl2 solution.
a!
Electronic mail: wlcai@ustc.edu.cn
The morphology of the as-prepared porous alumina
membranes was observed using an atomic force microscope
@~AFM! Park Scientific Instruments, Autoprobe CP# and a
scanning electron microscope @~SEM!, Hitachi X-650#. AFM
photographs of the surfaces of porous alumina membranes
prepared in C2H2O4 or H2SO4 are shown in Fig. 1. From Fig.
1, ordered pore arrays of about 35 and 25 nm in diameter can
be seen for porous alumina prepared in C2H2O4 and H2SO4,
respectively. The SEM photograph of the cross section of the
porous alumina membrane prepared in C2H2O4 is displayed
in Fig. 2. It shows nonintercrossing and parallel cylindrical
holes with a high aspect ratio.
A subsequent heat treatment or aging of the porous alu-
mina membrane was undertaken. After heat treatment, pho-
toluminescence spectra of porous alumina membranes were
measured using a visible–ultraviolet spectrophotometer ~Hi-
tachi 850! with a Xe lamp as the excitation light source at
room temperature. The excitation wavelength was 360 nm
and a 390 nm filter was used. Figure 3 presents the PL spec-
tra of the porous alumina membrane with a remaining alu-
minum layer prepared in C2H2O4 ~sample A! in the wave-
length range of 400–600 nm. The PL spectrum of a porous
Si sample is also shown in Fig. 3 for comparison. Clearly, a
blue PL band appears in each curve for sample A. The in-
tensity of the PL band increases with the heat-treatment tem-
FIG. 1. AFM photographs of surfaces of porous alumina membranes pre-
pared in C2H2O4 ~a! and in H2SO4 ~b!, respectively.

0003-6951/99/74(20)/2951/3/$15.00 2951 © 1999 American Institute of Physics

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2952 Appl. Phys. Lett., Vol. 74, No. 20, 17 May 1999 Du et al.

FIG. 4. Photoluminescence spectra of a porous alumina membrane prepared

in H2SO4 ~sample C!. ~a! As prepared; ~b! 200 °C34 h; ~c! 300 °C34 h;
~d! 400 °C34 h; and ~e! 500 °C34 h.

FIG. 2. SEM view of the cross section of a porous alumina membrane arrays present a blue PL band? Electron paramagnetic reso-
prepared in C2H2O4. nance ~EPR! measurements of the porous alumina membrane
prepared in C2H2O4 demonstrate that an obvious EPR signal
perature T a first, reaches a maximum when T a 5500 °C, and with g factor of 2.0085 appears in the EPR spectrum, as
shown in Fig. 5. This implies that in porous alumina mem-
then decreases after heating at 550 °C for 4 h. The intensities
branes exist many singly ionized oxygen vacancies (F 1 cen-
of the PL band for sample A do not change with either aging
ters! because other oxygen vacancies ~F and F 11 centers!
at room temperature for 15 days or annealing at 550 °C in H2
are not paramagnetic. Some authors6 have reported that F 1
for 1 h. Moreover, it should be pointed out that the PL in-
centers in Ti:Al2O3 crystal cause a blue PL band. Therefore,
tensity for sample A after heating at 500 °C for 4 h is much
it can be deduced that the blue PL band of porous alumina
higher than that for porous Si measured under the same
membranes arises from F 1 centers.
condition.5 The intensities and peak positions of the PL band
With the rise of T a up to 500 °C for sample A and
for a porous alumina membrane prepared in C2H2O4 without
400 °C for sample C, substantial enhancement of the PL
a remaining aluminum layer ~sample B! before and after heat
band ~see Figs. 3 and 4! is tentatively ascribed to the follow-
treatment at 500 °C for 4 h are just the same as those for
ing factors. During heat treatment, oxygen in porous alumina
sample A under the same treatment condition. This indicates
membranes and oxygen diffusing from air into the mem-
that the remaining aluminum layer does not affect the PL
branes react with the remaining aluminum in alumina mem-
behavior of the porous alumina membrane. For the porous
branes, to form new alumina, and it is possible that in the
alumina membrane prepared in H2SO4 ~sample C!, a similar
newly formed alumina exist many oxygen vacancies. In ad-
PL phenomenon is observed, as shown in Fig. 4. It can be
dition, when the formation rate of the new alumina is higher
seen that the intensities of the PL band are much weaker than
than that of the oxygen diffusing into the porous alumina
those for sample A, and the highest intensity for sample C
membrane, the oxygen reacting with the remaining alumi-
appears at lower temperature.
num is mainly provided by the porous alumina membrane
Why do porous alumina membranes with ordered pore
itself. This also causes oxygen vacancies in the alumina
membrane to increase dramatically. The increase of oxygen
vacancies leads F 1 centers to increase because an F 1 center
is formed by an oxygen vacancy trapping an electron. This is

FIG. 3. Photoluminescence spectra of a porous alumina membrane prepared

in C2H2O4 ~sample A!. ~a! As prepared; ~b! 200 °C34 h; ~c! 300 °C
34 h; ~d! 400 °C34 h; ~e! 500 °C34 h; ~f! 550 °C34 h; ~g! aging in air
for 15 days after heating at 550 °C for 4 h; ~h! annealing at 550 °C in H2 for FIG. 5. X-band ~9.47 GHz! EPR trace at room temperature for porous alu-
1 h after aging in air for 15 days; and ~i! porous Si. mina prepared in C2H2O4.
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Appl. Phys. Lett., Vol. 74, No. 20, 17 May 1999
why the intensity of the blue PL band is raised first with
increasing T a . With further increasing T a the PL intensity of
porous alumina membranes becomes weak suddenly ~see
Figs. 3 and 4!. This is because at higher T a the annihilation
rate of oxygen vacancies becomes faster than the formation
rate, so that only a few F 1 centers remain in porous alumina
membranes. It results in the PL intensity dropping dramati-
cally.
When T a rises, the peak position of the PL band exhibits
blueshifts ~see Figs. 3 and 4!. This can be explained as fol-
lows. With increasing T a , two factors may affect the peak
position. One is the redshift factor and the other is the blue-
shift one. The elevation of T a apparently leads to an increase
of oxygen vacancies in the porous alumina membranes. This
may cause the PL band to present redshifts. For example,
Philipp7 has observed that with increasing oxygen vacancies,
the band gap of silica becomes narrow dramatically. There-
fore, it is supposed that the increase of oxygen vacancies in
porous alumina membranes may induce the band gap of alu-
mina to become narrow. Since the energy levels of F 1 cen-
ters are located in the band gap of alumina, with increasing
oxygen vacancies the decrease of the band gap of alumina
will induce the spacings of the energy levels of F 1 centers to
become narrow. It will lead the PL band, which originated
from electronic transitions between the energy levels of the
F 1 centers, to move towards the long wavelength ~redshifts!.
On the other hand, a blueshift factor plays an important role
with increasing T a at the same time. The volume expansion
of the porous alumina during oxidation was observed by Jes-
sensky, Müller, and Gösele.8 This implies that the volume of
the alumina formation regions expands, but the volume of
the remaining aluminum in the alumina membranes does not
expand. As a result, an internal stress which prevents the
volume expansion of alumina is established in the alumina
membranes. The internal stress will cause the band gap of
the alumina to become narrow,9 and hence, the spacings of
the energy levels of the F 1 centers decrease. This leads the
PL band to present redshifts in comparison with that of the
alumina membrane without the remaining aluminum layer.
With increasing T a , the remaining aluminum is gradually
oxidized to form alumina, resulting in the decrease of inter-
nal stress. Therefore, the redshift effect drops. In other
words, the blueshift effect increases. As a result, when this
blueshift effect exceeds the redshift effect caused by the in-
crease of oxygen vacancies, the PL band presents blueshifts
with increasing T a .
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Du et al. 2953
The intensities of the PL band for the porous alumina
membranes prepared in C2H2O4 ~sample A! are higher than
those for the porous alumina prepared in H2SO4 ~sample C!
~see Figs. 3 and 4!. This is probably because the oxidation
activity of H2SO4 is much stronger than that of C2H2O4,
resulting in very few oxygen vacancies existing in the as-
prepared sample C. This supposition is not inconsistent with
the experimental results. The as-prepared sample C does not
exhibit the PL band, while the as-prepared sample A shows
an obvious PL band ~curve a in Figs. 3 and 4!.
For sample A, aging at room temperature and annealing
in H2 do not cause the PL intensity to change. This suggests
that in porous alumina membranes after being heat treated
several times, the F 1 centers and the Al–O bonds become
stable. Therefore, the numbers of F 1 centers almost do not
change, neither are they created nor annihilated.
In conclusion, porous alumina membranes with ordered
pore arrays prepared electrochemically from Al metal in ei-
ther C2H2O4 or H2SO4 present a blue PL band. This PL band
apparently arises from the singly ionized oxygen vacancies
(F 1 centers! in alumina membranes. With increasing heat-
treatment temperature T a , the blueshift of the PL band is
ascribed to the blueshift effect exceeding the redshift one.
This band being enhanced with the rise of T a is attributed to
the formation of new oxygen vacancies, and hence, the F 1
centers in porous alumina membranes. With further increas-
ing T a , the intensity of the PL band descends because of the
decrease of the F 1 centers.
The authors are grateful to the Climbing Program—the
key projects of the fundamental research of China, the Natu-
ral Science Foundation of China, and Chinese Academy of
Sciences for financial support.
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