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anodization
Kunbae Noh, Karla S. Brammer, and Hyunsu Kim
Materials Science and Engineering, University of California, San Diego, La Jolla, California 92093
Sungho Jina)
Materials Science and Engineering, University of California, San Diego, La Jolla, California 92093
(Received 8 June 2010; accepted 17 September 2010)
Anodized aluminum oxide (AAO), well-known hexagonally ordered vertical pore nanostructure,
can be altered to form nanotubular AAO arrays potentially having many favorable properties due to
its large surface area and unique geometry. We present here a creation of novel nanotubular AAO
structure by the hard anodization technique. Because of the guided formation of void channels
at triple cell junctions during the course of the controlled anodization process, periodically
spaced-apart aluminum oxide nanotubular geometry could be achieved over large areas. Further
separation to well-dened individual AAO nanotube arrays was obtained when etched in a mixed
CuCl2/HCl solution during Al substrate removal. Nanotubular geometry AAO with periodic and
mechanically robust structure can be useful not only for biomedical applications such as to enhance
cell adhesion and viability or drug delivery vehicles, but also as a large-surface-area catalyst support
or sensor elements.
186
I. INTRODUCTION
II. EXPERIMENTAL
A. Aluminum pretreatment and anodization
187
once more. The samples were then inverted onto coverslips, mounted, visualized, and photographed using a green
lter by a uorescence microscope. (DM IRB; Leica Co.,
Deereld, IL).
FIG. 3. SEM images showing: (a) top view of upside down barrier layer for the porous AAO after MA with 0.3 M sulfuric acid at 25 V, (b) porous
structure after the barrier layer is removed, (c) top view of upside down tubular AAO right after HA at 0.01 M sulfuric acid 40 V, (d) top view SEM
after the nanotube tip is etched away and the tubular geometry is realized. The schematics for porous AAO formation mechanism are presented on the
left of image (b) and the mechanism of nanotube formation is illustrated by the schematics on the right side of image (d).
FIG. 4. SEM image of freestanding AAO nanotubes placed onto Si substrate (after removal of Al substrate); (a) low and (b) high magnication,
respectively. Some of the loose nanotubes imply a mechanical robustness as they can be bent without fracture.
j 5 j0 exp bE
where both j0 and b are temperature- and materialdependent parameters and E is the effective electric eld.28
Another interesting observation regarding AAO nanotubes obtained in this work is that we can obtain highaspect-ratio (diameter to length) AAO nanotubes of
greater than ~1000. Some of the loose nanotubes in Figs.
4 and 5 indicate that the AAO nanotubes can have robust
mechanical properties as individual nanotubes can be seen
bent or curved without fracture. Because of the dielectric
nature of Al2O3 nanotubes, there is some electron charging
effect during SEM examination, which makes the image
slightly blurry at high magnication, Fig. 4(b). The sample
was anodized at 40 V using 0.01 M sulfuric acid, followed
by chemical etching by immersing in the mixed CuCl2 +
HCl solution for 4 h at 20 C for removal of Al substrate. A
pore-widening etching treatment removes the barrier layer
and reveals the nanotube geometry. Figure 5 shows the
189
FIG. 5. Oblique view of SEM image of vertically aligned periodic AAO nanotubes. (a) Low magnication image, (b) high magnication image
showing the nanotube and hole dimension, (c) cross-sectional SEM showing the aligned nature of the AAO nanotubes and an example bent
(mechanically exible) behavior of a separated individual alumina nanotube. Highly ordered hexagonal arrangement was obtained by HA (at 40 V
with 0.01 M sulfuric acid), followed by chemical etching in 5 wt% phosphoric acid.
FIG. 6. SEM images of vertically aligned periodic AAO nanotubes as (a) hard-anodized, tip-closed nanotube geometry, (b) after chemical etching to
open the nanotube tip, and (c) after additional Cr sputter deposition to intentionally reclose the nanotube entrance. An intermediate, partially blocked
nanotube structure is obtained if the sputtering time is reduced.
FIG. 7. Osteoblast (bone) cell viability determined by FDA (live uorescent staining, green color) after 24 h of culture time on (a) at Al2O3 and on
(b) Al2O3 nanotubes. Clearly, the cell adhesion/spreading are signicantly enhanced on the nanotube surface. (c) Oblique view SEM image of
vertically aligned highly periodic AAO nanotubes for cell culture.
release. Alternatively, a postdeposition of additional material onto the open nanotubes can be used to partially or
completely block the nanotube entrance. An example is
shown in Fig. 6(c) where it is shown that the use of
chromium sputter deposition can lead to the intentional
blockage of the nanotube entrance, as shown in Fig. 6(c).
The amount of Cr sputtering can be adjusted to achieve any
desired nanotube pore entrance dimension for a selected
drug release rate.
For cell growth and proliferation for various biomedical applications such as tissue engineering, bone growth,
stem cell differentiation control, an important rst step is
for the cells to adhere strongly on the substrate. Such
strongly adhered/anchored cells are likely to function
more actively and proliferate better. Nanostructured architechure of this nature can be used in various biological
applications, such as implant surface coatings for enhanced
cell activities. It is well known that the oxide layer on
metallic implants is responsible for the bone bonding and
natural bone integrating characteristics of orthopedic
implants.36 Therefore, new research aims have recently
been geared toward optimizing these properties to promote
enhanced osseointegration37 by modifying and improving
this oxide layer. Oxide nanostructures such as vertically
aligned nanotubes can provide signicantly enhanced osteoblast cell adhesion and bone growth, for example, TiO2
nanotubes near the dimension of ~80100 nm diameter.38,39
Therefore, we have also investigated the potential use of our
alumina nanotube array structure as an implant surface
191
IV. SUMMARY
Highly hexagonally ordered, vertically parallel aluminum oxide nanotube array was fabricated via the HA
technique. Due to the high current anodizing process,
noticeable voids are formed along the AAO cell boundaries located at triple cell junction, which enhances the
separation of adjacent nanotubes during the pore-widening
process.
The Al2O3 nanotube arrays as fabricated exhibit a uniform and reproducible dimension, and a quite high aspect
ratio of greater than ~1000. The nanotubes appear to be
mechanically exible. Such high-aspect-ratio, mechanically robust, large-surface-area nanotube array structure
can be useful for many technical applications, including
shear tactile sensors, efcient catalyst supports, chemical
reactant releasing materials, and drug storage and slow
release biomedical devices.
ACKNOWLEDGMENTS
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