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Highly self-assembled nanotubular aluminum oxide by hard

anodization
Kunbae Noh, Karla S. Brammer, and Hyunsu Kim
Materials Science and Engineering, University of California, San Diego, La Jolla, California 92093

Se-Yeon Jung and Tae-Yeon Seong


Department of Materials Science and Engineering, Korea University, Seoul, Korea

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.

Address all correspondence to this author.


e-mail: jin@ucsd.edu
DOI: 10.1557/jmr.2010.6

and bimodal17 geometries by using modied anodizing


parameters. HA techniques with high current densities
involved, have several key advantages over conventional
mild anodization (MA), such as an ultrafast growth rate and
improved controllability, and hence can provide highly
ordered AAO structures that could not be obtained previously using MA techniques. These enhanced nanostructures could open up new opportunities for advanced device
applications.
Alumina in a nanotube conguration is of particular
interest due to its unique structure and outstanding
materials properties. We have recently investigated periodically spaced-apart aluminum oxide nanotubes as
a potential candidate for drug loading and controlled
release vehicles for biomedical applications,18 in particular orthopedic implant application. In comparison to
nanoporous structure often seen in the HA alumina,13
nanotubular conguration was observed in our samples.
Nanotubular AAO obtained by a combination of HA
technique and subsequent chemical etching process, contains much more active surface areas than in porous AAO
due to inside and outside wall surfaces, possibly improved
mechanical exibility due to separated conguration, and
in addition has smaller diameter features (~20 nm) with
a uniform size distribution. In this report, we demonstrate
that individual separation of AAO nanotubes is achieved
by chemical etching, and that selective opening and
closing of the nanotube entrance can be accomplished
with novel self-assembly processing.

186

Materials Research Society 2011

I. INTRODUCTION

Since the discovery of self-ordered porous alumina in


1995,1 anodized aluminum oxide (AAO) has become one
of the most popular periodic templates to create lowdimensional materials such as nanodots, nanowires, and
nanotubes for various nanotechnology applications.2,3
More recently, some efforts have been made to use AAO
as a material for implant surface coatings on Ti-based
substrates for enhanced bone in growth,4 stent coating,5 and
drug delivery6 because of its pored structures together with
the biocompatible properties of aluminum oxide.
It is well known that ordered porous AAO can be
obtained in broad processing windows. Masuda and coworkers7 reported ordered porous AAO in several selfordering regimes, i.e., 25 V in sulfuric acid, 40 V in oxalic
acid,1 and 195 V in phosphoric acid.8 In addition, Lee and
co-workers913 recently reported a new self-ordering regime: 110~140 V in malonic acid and 110~150 V in oxalic
acid, which drew renewed attention to a hard anodization
(HA) process associated with high anodic currents and
formation of unique nanoarray structures.
In addition to regular porous AAO, various novel AAO
nanostructures were reported in the literature such as
modular,10 serrated,14 perforated,15 pore size-oscillated,16
a)

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K. Noh et al.: Highly self-assembled nanotubular aluminum oxide by hard anodization

As an exemplary potential application, we also show


enhanced osteoblast cell adhesion and spreading on
nanotube congured AAO surfaces. In terms of topographic effects on bone cell (osteoblast) behavior, it has
been shown that ceramics, such as alumina, with textures
on the nanoscale, created by AAO, exhibit enhanced
effects on growth rates and bone-forming ability.4,19,20
Many orthopedic biomaterial researchers use the typical
AAO nanotexturing technique, focusing on the porous
structures effect on osteoblast behavior to design a better
oxide surface for bone implants. In this work, however, we
choose to use an alternative porous structure, namely AAO
nanotubes, as a new method for probing osteoblast
adhesion for potential use as an implant surface coating.

II. EXPERIMENTAL
A. Aluminum pretreatment and anodization

A 0.5 mm thick annealed Al foil purchased from Alfar


Aesar (Ward Hill, MA; 99.99%) was used as the starting
material. The Al foil was successively degreased by
isopropyl alcohol and acetone with ultrasonication followed by a deionized water rinse and nitrogen gas blow.
The Al foil was slightly etched in 1 M NaOH aqueous
solution to remove any possible surface contaminations
before the electropolishing process conducted at 20 V in
a solution of perchloric acid (70%) and ethanol (99.9%)
(1:4 volume ratio) at 5 C using a Pt counter electrode.
To prevent nonuniform oxide growth during HA,
porous AAO (1~2 lm thick) layer was formed rst at
25 V in 0.3 M sulfuric acid, and then the concentration of
electrolyte was diluted to 0.06 M (for 35 V anodization)
and 0.01 M (for 40 V anodization), and the voltage was
slowly increased from 25 V to target voltage (VT), and was
then maintained at VT with vigorous stirring to dissipate
heat evolution due to high current until the anodization
process was completed. The electrolyte temperature was
maintained at 1 C during both mild and hard anodization
processes using a powerful refrigeration bath (Thermo
Scientic, NH; NESLAB RTE7) in which the coolant
circulates in a double-wall glass chamber. The power
supply (Agilent, CA; E3612A) was connected to a digital
multimeter (Keithley, OH; Model 2100) to monitor and
record voltage-current evolutions.
After the anodization process, the top side of the AAO
layer was glued onto Si substrate using thermoplastic
adhesive (Electron Microscopy Sciences, PA; crystalbond)
for ease of handling. The Al substrate that supported the
AAO layer was then selectively etched and removed using
a mixed HCl and CuCl2 solution for a few tens of minutes
until the reaction ended. The AAO barrier layer near the
bottom of the anodized pores (now the top surface as the
sample was mounted upside down on Si substrate) was then
removed by pore-widening chemical etch solution (5 wt%

phosphoric acid). The microstructure was then examined


under scanning electron microscope (Phillips; XL30 ESEM).
Overall fabrication processes are schematically illustrated in
Fig. 1. The Cr sputter deposition was performed using direct
current sputtering for a nominal thickness of ~5 nm.
B. Cell culture assay for adhesion and viability

For cell culture studies, MC3T3-E1 mouse osteoblast


(CRL-2593, subclone 4, ATCC, Manassas, VA) bone cells
were used. Cell growth media consisted of alpha minimum
essential medium (a-MEM; Invitrogen, Carlsbad, CA) in
the presence of 10% fetal bovine serum (FBS; Cellgro,
Antioch, IL) and 1% penicillin-streptomycin (PS; Invitrogen). The cells were incubated under the standard 37 C,
5% CO2 environment. When the concentration of the
MC3T3-E1 osteoblastic cells reached ~3  105 cells/mL,
they were seeded onto the substrate of interest (electropolished at Al versus AAO nanotube surface), which were
placed individually in a 12-well polystyrene plate and
stored in a CO2 incubator for 24 h. The concentration of
the cells seeded onto the specimen substrate was ~5  104
cells/well. Next, to observe cell adhesion, spreading,
morphology, and viability of the attached cells, a uoroscein
diacetate (Sigma, MO; FDA) staining was conducted. The
cells on the substrates were washed with 1X PBS (phosphate-buffered solution pH 7.4, Invitrogen) and incubated
for ~5 min with FDA stock (5 mg dissolved in 1 mL
acetone) dissolved in 1X PBS (10 lL/10 mL), and washed

FIG. 1. Schematic illustration of nanotubular AAO fabrication. (a) MA


to form porous AAO layer in 0.3 M sulfuric acid, (b) HA to form tubular
AAO layer, (c) selective aluminum removal by etching in (CuCl2 + HCl)
solution, (d) attaching AAO upside down on Si substrate and porewidening etch in 5 wt% phosphoric acid.

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K. Noh et al.: Highly self-assembled nanotubular aluminum oxide by hard anodization

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).

III. RESULTS AND DISCUSSION

Conventional MA for AAO formation is associated


with a relatively low current density over the entire
anodizing period, but there is an initial current jump
followed by a rapid drop within a few tens of seconds at
the beginning stage. In the case of HA, however, a large
amount of current ows at the beginning and it is slowly
decreased over the anodizing time span, as shown in
Fig. 2. High current during the HA process ensures not
only fast AAO lm growth but also highly ordered AAO
cells, as will be discussed later. However, it is worthwhile
to mention that samples should be preanodized in MA
condition to produce a certain thickness of porous AAO
lm layer before HA. Otherwise, undesirable local oxide
thickening or dielectric breakdown can readily occur
during HA.
The SEM micrographs in Fig. 3 compare conventional
porous AAO and newly obtained nanotubular AAO by
HA and nanotube tip etching. In the case of conventional
porous AAO, hexagonally ordered AAO pores are vertically grown in the underlying Al substrate under the wellknown self-assembly condition. The pore channels are
straight and parallel to each other, and the bottom of each
vertical pore is closed with a hemispherical end that forms
a continuous oxide layer over the whole anodized area,
which is known as a barrier layer,21 as indicated in Fig. 3
(a). The SEM image in Fig. 3(a) represents the top view of
the upside down barrier layer for the porous AAO sample
after MA with 0.3 M sulfuric acid at 25 V. The porous
AAO structure after the barrier layer is removed is given in
Fig. 3(b).

FIG. 2. Representative anodic current changes during anodization


experiments. MA (black dotted line) was conducted at 25 V in 0.3 M
sulfuric acid at 1 C, and HA (red solid line) was conducted at 40V in
0.01 M sulfuric acid. MA for 30 min led to the porous AAO structure,
which was used as the basis to start the subsequent HA.
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In the case of HA, the barrier layer exposed after the Al


substrate removal contains a signicant depth of recessed
voids, which were formed at between-cell triple junctions, as shown in Fig. 3(c). The image of Fig. 3(c) was
obtained by HA at 0.01 M sulfuric acid 40 V. The SEM
image in Fig. 3(d) is obtained after the nanotube tip is
etched away and the tubular geometry is realized. The
mechanisms of microstructural formation for porous AAO
versus alumina nanotubes are schematically illustrated on
the left of image (b) and on the right of image (d),
respectively.
The void structure in Fig. 3(c) appears to play
a signicant role in the separation of neighboring AAO
nanotubes from each other during pore-widening chemical etching, as seen in Figs. 3(c) and 3(d). Voids were
often observed at the triple cell junctions especially after
the HA. Possible mechanisms for void formation were
proposed by several groups,11,17,2227 which can be
summarized as follows: (i) electrochemically unfavorable oxygen gas formation and their entrapment along
cell boundaries during fast AAO growth; (ii) compositional difference between inner and outer pore wall,
which can lead to a different dissolution rate in porewidening solution; (iii) lower density at triple cell
junction due to repulsive force arising from volume
expansion during HA; and (iv) accumulated compressive
stress along the cell boundaries, and combination of the
above. We presume that our nanotube structure formation
is based on one or more of these mechanisms. By virtue
of the existence of void channels, pore-widening solution
could now penetrate through void channels and, therefore, could etch the outer pore walls helping to completely separate the nanotubes from each other. The
etching of the inner wall of the AAO cell was retarded
due to the closed conguration of the barrier layer at the
beginning of pore-widening treatment. Later, when the
nanotube tip is dissolved away, the etching solution
could wet the inner pore walls and start etching the walls
(see the schematic illustrations in Fig. 3).
Our well-separated nanotube array structure, Figs. 36,
could be attributed to different dissolution rates of inner
versus outer pore walls due to their compositional difference. In addition, the presence of the barrier layer covering
the nanotube tip (after removing the Al substrate material)
delays the inner wall etching while outer pore walls are
continuously being etched through void channels at the
triple junctions from the very beginning of the chemical
etching, which makes it possible to obtain a good nanotube
separation from each other.
Highly ordered AAO nanotube formation as reported
in this work could be associated with high current
evolution, directly related to high electric eld across
barrier layer near the pore bottom. The current density
during anodization is dependent on various parameters
and the applied electric eld, i.e.,

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K. Noh et al.: Highly self-assembled nanotubular aluminum oxide by hard anodization

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

low magnication and high magnication SEM images of


the AAO nanotubes.
In previous research described in the literature, various
attempts have been made to obtain individual Al2O3
nanotubes, for example, by using atomic layer deposition
of aluminum oxide material on organic nanowires,29
partial chemical dissolution and ultrasonic vibration of
porous AAO,30 and hydrothermal synthesis.31 However,
these methods to obtain isolated AAO nanotubes are
somewhat complicated and have various processing and
structural limitations when high-aspect-ratio nanotubes
are needed. Our HA-based approach is a convenient
technique for fabrication of alumina nanotubes having
uniform tube diameter and tailored tube length. It would be
interesting to take these individual Al2O3 nanotubes for
mechanical property evaluations and related nanomechanics studies.
The Al2O3 nanotube arrays that we have fabricated
exhibit uniform and reproducible dimensions, and a quite
high aspect ratio (diameter of ~80 nm, height of ~100 lm,

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K. Noh et al.: Highly self-assembled nanotubular aluminum oxide by hard anodization

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.

aspect ratio .~1000). The SEM micrographs in Fig. 5


clearly indicate the high aspect ratio. It is also seen that the
Al2O3 ceramic nanotubes, if individually separated, can be
mechanically exible. Such a exible nature can be useful
for using the Al2O3 nanotube array as a component of
tactile shear sensors for robotics, air of uid ow sensors,
and security sensors, similarly as with carbon nanotube
shear sensors.32,33 These aligned Al2O3 nanotubes can be
surface metalized with highly conductive metals or magnetic materials, e.g., by sputter deposition or atomic layer
deposition, for various other applications such as electron
190

eld emitters, electrical interconnects, and sensors and


actuators.
Such high-aspect-ratio nanotubes provide a very large
surface area, especially since both the inside and outside
diameter surfaces can be used, which is not the case for
simple AAO pore structures. The large surface area can
be exploited for enhanced catalytic reactions (if surfacecoated with a very thin catalyst material such as Pt), and
can assist in increasing the amount of drug molecules
adsorbed on the surface. Together with the large empty
space within the nanotube pores as well as the space

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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.

between the nanotubes in the high aspect nanotube


bundles, this can be useful for storage of drugs and other
chemicals for controlled slow release, similarly as for the
vertically aligned Si nanowire array structure.34
As an example of potential applications, a model antibiotics drug, amoxicillin whose size is small35 (~0.8 nm)
was loaded into the Al2O3 nanotubes, and drug release
experiments were conducted. Preliminary data indicates that
a controlled and sustained drug release can be accomplished
for a long period of time extending over ve weeks, which is
a promising trend. The details of the drug release study will
be reported in future publications. Factors affecting sustained release of drugs or catalyst molecules from the AAO
nanotubes include the physical dimension of nanotube
storage space, such as diameter, length, and surface area
as well as the surface chemistry of platform and its interaction with the stored material itself. Alteration of the
nanotube pore entrance dimension could also be important;
for example, an intentional partial blockage of the nanotube
pore entrance can be contemplated using a deposition of
organic or inorganic material to reduce the diffusion rate of
drug release. Shown in Figs. 6(a)6(c) is an example
manipulation of nanotube pore entrance dimension by
processing approaches. The pore-widening process for the
AAO nanotubes opens up the nanotube tip completely, as
shown in Fig. 6(b). Of course, a partial nanotube tip opening
can be obtained by shorter time pore-widening treatment so
as to provide a smaller diameter nanotube entrance, which
would certainly enable a slower-rate, time-extended drug

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

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K. Noh et al.: Highly self-assembled nanotubular aluminum oxide by hard anodization

coating by employing an in vitro cell adhesion assay. Shown


in Fig. 7 are comparative osteoblast (bone) cell adhesion
images for at Al2O3 control substrate [Fig. 7(a)] versus
Al2O3 nanotube arrays [Fig. 7(b)]. An FDA viability marker
was used to stain the cytoplasm of osteoblast cells cultured
on the different surfaces.
Osteoblast (bone) cell adhesion after 24 h of culture
time is much more pronounced on the Al2O3 nanotube
substrate compared to a at Al2O3 control substrate, and it is
evident that the cell adhesion and spreading is signicantly
enhanced on the nanotube surface. These primary studies
suggest that the AAO nanotube surface used as a possible
orthopedic implant surface is an attractive template for
improving the osteoblast response. The AAO nanotube
surface, with a wide array of congurations, sizes, and
shapes, can be useful for parallel experiments looking
further into osteoblast response, functionality, and matrix
production for improved osseointegration. The oblique
view SEM image of vertically aligned, highly periodic
AAO nanotubes used for the osteoblast cell culture is shown
in Fig. 7(c). The nanotube sample was anodized at 35 V
using 0.06 M sulfuric acid. The pore-widening treatment
was conducted with 5 wt% phosphoric acid at 20 C.

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

We wish to acknowledge the nancial support of this


work by NSF-Nanomanufacturing Division (CMMI No.
0856674), CMRR (Center for Magnetic Recording Research) at UC San Diego, National Research Foundation
(NRF) grant through World Class University Program
(R33-2008-000-10025-0), Air Force Ofce of Scientic
Research-Ministry of Science and Technology (AFOSRMOST) Program, and Center for Nanostructured Materials Technology (CNMT) Grant Frontier R&D Program.
192

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