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The Anodization of Aluminum for Nanotechnology Applications

Article in JOM: the journal of the Minerals, Metals & Materials Society · June 2010
DOI: 10.1007/s11837-010-0088-5

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 Corrosion Overview

The Anodization of Aluminum for

Nanotechnology Applications
Woo Lee

In light of the ever-increasing demand oxide can be imparted to the aluminum to anodic oxidation. The anodic pro-
for the development of an effective, or its alloys by subjecting the metal cess also provides a suitable surface
inexpensive and technologically simple or base for subsequent electroplating,
method, a naturally occurring self-orga- How would you… painting and decorative coloration by
nization of oxide nanopores during the incorporation of pigments followed by
…describe the overall significance
anodization of aluminum has recently of this paper? sealing of the anodized materials.
attracted a vast amount of research at- This article conveys some of the This electrochemical process has
tention in the field of nanotechnology. latest advances in anodization of recently drawn a renewed attention in
This article gives a brief overview on aluminum, which has long been an academic research, especially in the
some of the recent advances in the indispensible process in the surface field of nanotechnology. An idealized
finishing industry, but now becomes
anodization of aluminum, focusing one of the most important processes structure of nanoporous anodic alum-
on the fabrication of highly ordered in nanotechnology for developing inum oxide (AAO) is schematically
nanoporous anodic aluminum oxide. advanced nanodevices. shown in Figure 1c. Anodic aluminum
Conventional anodization, newly …describe this work to a oxide formed by porous-type anodization
developed hard anodization, pulse materials science and engineering under a controlled electrochemical
anodization process, and generic ap- professional with no experience in condition is characterized by a large
your technical specialty?
proaches for the fabrication of three- number of non-interconnecting paral-
This article is an introduction to
dimensional pore structures with pe- anodization of aluminum, which
lel pores extending through the film to
riodically modulated diameters are is a subject of electrochemistry. the oxide/metal interfaces, where each
discussed. Anodization of aluminum under a cylindrical nanopore is closed by a thin
controlled electrochemical condition barrier oxide layer with hemispherical
INTRODUCTION yields ordered porous alumina with
a close-packed hexagonal array geometry. Each pore and the region
Anodization is an electrochemical of cylindrical nanochannels. The surrounding it comprise a hexagonal
oxidation process employed to increase diameter, density, and aspect ratio cell. These cells are self-organized in
the thickness of the native oxide layer of pores can be tightly controlled by the form of a hexagonally close-packed
varying the anodization condition,
on the surface of metals (e.g., Al, Ti, Hf, which makes the porous anodic structure, like a honeycomb.6 Based on
W, Nb, Sn, Zr, etc.) or semiconductors alumina an important platform the recent development, self-ordered
(e.g., Si, InP, GaAs, etc.) (Figure 1a).1–3 in nanotechnology for developing nanoporous AAOs with a uniform pore
various functional nanostructures. diameter in the range of 20–400 nm
Among anodizable materials, aluminum
has been of particular interest due to its …describe this work to a and with a pore density in the range of
many profitable engineering properties. layperson? 108–1010 pores/cm2 can conveniently be
In general, anodization of aluminum Anodization of aluminum, prepared by anodization of aluminum.
an electrochemical oxidation
can result in two different types of of aluminum, can produce a
The depth of straight nanopores can
anodic oxide depending on the nature honeycomb-like nanoporous oxide easily be controlled in the range of a
of an electrolyte used; a compact and film. The process was developed few tens of nanometers to more than
non-porous barrier-type oxide from for the protection of seaplane parts several hundred micrometers by varying
from corrosive seawater in 1923.
neutral electrolytes and a porous-type The products of the process can be the anodization time. Due to the unique
oxide from acidic electrolytes (Figure found everywhere around us, for structural feature of nanoporous AAO
1b).3 Over the last several decades, example in cookware, architectural and also to the tailoring capability of its
the process, particularly porous-type items, vehicles, and machine parts. structural parameters, the anodization
Now nanotechnology scientists
anodization, has raised substantial are paying attention to this nearly process has attracted scientific attention
technological interest in the industry.4,5 century-old process for developing in the use of the resulting AAO not only
Many desirable properties such as various functional nanostructures. as template for fabricating structurally
This article gives a brief overview on well-defined nanostructures (e.g.,
higher thickness, hardness, good
the recent progress in the anodization
corrosion resistance, higher abrasive of aluminum. arrays of nanodots, nanotubes, and
and wear resistance over the native nanowires) in a large quantity,7–12 but

Vol. 62 No. 6 • JOM www.tms.org/jom.html 57

 as a starting material for developing
Rectifier high-performance sensor, biomedical,
Al2O3
Barrier-type
photonic, energy harvesting, and
Anodization memory devices.13–17
Oxide MILD ANODIZATION

Electrode
Film Al Pore
Metal

Al2O3 Over the past several decades, studies

on aluminum anodization have been
Porous-type
Electrolyte Bath driven by the aluminum industry, and
Anodization
thus mostly devoted to the improvement
of technical quality of the anodic films
Pore
Cell Boundary for various commercial applications
Cell and also to the production at an efficient
rate and cost. Although a wide variety of
anodization processes and proprietaries
have continued to be developed in
Porous Layer

industry, the spatial ordering and the

uniformity of pores in anodic oxide
films have not been a matter of concern.
Barrier Anodic oxide films produced by a
Layer typical industrial process, which is
Aluminum represented by hard anodization (HA),
are characterized by non-uniform pore
structures with numerous micrometer-
Figure 1. Schematic illustrations showing (a) a simplified anodization setup, (b) two different
types of aluminum anodization, and (c) an idealized structure of anodic aluminum oxide
sized cracks. Thus, they are not suitable
(AAO) produced by a porous-type anodization. for nanotechnology applications.
In 1995, Masuda and Fukuda

500
H2SO4
ζMA = 2.5 nmV−1
400 H2C2O4
H3PO4
300
Dint (nm)

200
ζHA = 1.8−2.0 nmV−1
100

0
0 50 100 150 200
Anodization Potential (V)

Figure 2. (a) A schematic procedure of a conventional two-step mild anodization (MA) for self-ordered anodic aluminum oxide (AAO).
(b–d) Representative SEM micrographs of self-ordered AAOs produced by MA using (b) 0.3 M H2SO4 at 25 V, (c) 0.3 M H2C2O4 at 40
V, and (d) 1 wt.% H3PO4 at 195 V. (e) A color-coded SEM image of AAO formed by two-step MA using 0.3M H2SO4 at 25 V, showing a
poly-domain structure (Reprinted with permission from Reference 44 © 2008 American Chemical Society). An area with the same color
consists of a domain. Pores that have no apparent hexagonal coordination (i.e., defect pores) are marked white. (f) Summary of self-
ordering potentials and the corresponding interpore distance (Dint) in mild anodization (MA) and hard anodization (HA).

58 www.tms.org/jom.html JOM • June 2010

found that AAO formed by long- dependent on the applied potential (U) self-organized formation of oxide
term anodization (t ~ 160 h) under a with proportionality constants ζ = 2.5 nanopores. For self-organized growth
potentiostatic condition (U = 40 V) nmV–1 for Dint and η = 1.2 nmV–1 for of AAOs, mechanical stress at the
using 0.3 M oxalic acid exhibits a self- tb (Figure 2f).6,21,24,28 Pore diameter (Dp) metal/oxide interface that is associated
ordered cell configuration at the bottom has also been known to increase at a with volume expansion during
part of AAO as a consequence of gradual rate of ca. 1.3 nmV–1.26 But the potential oxidation of aluminum was proposed
rearrangement of the cells initially in a dependence of Dp is not as sensitive as as a main driving force for the close-
random configuration.18 They reported the interplay between the current density packed hexagonal arrangement of
that the size of the defect-free domain, in and the temperature, concentration and oxide nanopores.21,34 It is generally
which pores are almost ideally arranged nature of the electrolyte used.30–32 For accepted for steady-state film growth
forming a honeycomb structure, the self-ordered AAO formed under that oxide nanopores are generated
increases with the anodization time MA conditions, Nielsch et al. proposed as results of a dynamic equilibrium
but is limited to several micrometers.18 an empirical rule that self-ordering of between the rate of field-assisted oxide
This experimental observation led porous alumina requires a porosity dissolution at the electrolyte/oxide
to the development of the ‘two- (P) of about 10% irrespective of the (e/o) interface and the rate of oxide
step anodization’ process, by which anodizing potential and composition of formation at the metal/oxide (m/o)
nanoporous AAO with highly ordered electrolyte and anodization conditions; interface, which keeps the thickness
arrangement of uniform nanopores can P(%) = the surface area ratio of pores to of the barrier layer constant.22,26,30,35,36
be obtained (Figure 2a).19 Since then, the whole oxide film = (π/23)(Dp/Dint)2 However, this dissolution-based pore
anodization of aluminum has drawn × 100.24 But there are some reports formation mechanism has been disputed
renewed attention, particularly in the that self-ordered AAOs can be attained many experiments. Oxygen isotope
field of nanotechnology research for the at other porosity (P) values ranging (18O) studies indicated that the pore
application of highly ordered AAO to from 10% to 30% depending on MA formation does not take place through
the development of various functional conditions.31,33 a simple oxide dissolution process, and
nanostructures. Many studies have been Anodization of aluminum has been suggested that pore formation consists
carried out in an attempt to improve the extensively studied over the last several of some kind of oxide decomposition
regularity of the pore arrangement, to decades. But there is still much work through the direct ejection of Al3+ into
control the size and position of the pores, to do in order to fully understand the the solution and the oxide formation
and to understand the development of
nanopores and their self-organizing
process during anodization of aluminum.
Much research effort has focused on
the exploration of optimum ordering
conditions for the electrolyte systems
(i.e., sulfuric, oxalic, phosphoric, and
chromic acid) that were investigated by
Keller et al. in the early 1950s.6
Ordered AAOs that are suitable for
nanotechnology applications have been
fabricated by mild anodization (MA)
of aluminum in a limited processing
window, known as ‘self-ordering
regime,’ under which self-organized
growth of ordered nanopores occurs
(Figure 2b–d): (i) sulfuric acid (H2SO4)
at 25 V for an interpore distance (Dint)
= 63 nm,20,21 (ii) oxalic acid (H2C2O4) at
40 V for Dint = 100 nm,18,20,21 and (iii)
phosphoric acid (H3PO4) at 195 V for
Dint = 500 nm.23 Many morphological
investigations revealed that structural
parameters (e.g., the pore diameter (Dp),
interpore distance (Dint), barrier layer
thickness (tb)) of AAOs formed under
self-ordering regimes depend primarily
on anodization potential (U),21,24,25 which Figure 3. (a) Schematic diagram of the fabrication of an ideally ordered anodic alumina using
an imprint stamp. (b,c) Typical SEM micrographs of long-range-ordered anodic alumina with
is in line with the earlier reports.6,26–29 (b) hexagonal and (c) square arrangements of nanopores. Magnified SEM images of the
The interpore distance (Dint) and the respective samples are shown as insets.
barrier layer thickness (tb) are linearly

Vol. 62 No. 6 • JOM www.tms.org/jom.html 59

at the m/o interface through oxygen of aluminum provides an effective appropriately tuning of the three well-
transport.37,38 Other experiments way to fabricate single-domain known acid electrolytes (i.e., H2SO4,
revealed that the field-assisted oxide AAOs. However, the major limitation H2CO4, and H3PO4) and searching new
dissolution at the pore base is virtu- of the process is that the attainable electrolyte systems. However, applied
ally negligible.39,40 In line with these maximum aspect ratio or depth of voltages higher than the optimum value
results, recent tungsten tracer studies nanochannels maintaining the initial required to maintain stable anodization
indicate that flow of oxide materials has hole configuration depends critically in a given electrolyte always result in
a major role in forming pores, contrary on anodization conditions.17 High “breakdown” or “burning” of the oxide
to expectations of a dissolution model aspect ratio of uniform nanopores film caused by catastrophic flow of
of pore development.41,42 The flow of can be obtained only under a narrow electric current coupled with a large
the oxide was suggested to arise from processing window (i.e., self-ordering amount of reaction heat.54
the field-assisted plastic flow of oxide regime), which practically limits the
HARD ANODIZATION
materials from pore base toward the cell range of selection over the interpore
boundary and the generation of stress distance (i.e., Dint = 63 nm, 100 nm, 500 Recently, Lee et al. showed that the
due to electrostriction and the oxidation nm for 25 V-H2SO4, 40 V-H2CO4, and self-ordering regimes can be extended
of aluminum. This flow-based pore 195 V-H3PO4 anodization, respectively). by implementing hard anodization
formation mechanism has been further When anodization is conducted (HA) of aluminum.55 The HA process
supported by theoretical study.43 outside the self-ordering condition, the was originally developed in the surface
Anodic aluminum oxide formed by initial degree of the spatial ordering finishing industry in the early 1960s,
two-step anodization under the self- defined by nanoindentation decreases and has been widely used for various
ordering regimes exhibit a poly-domain drastically. These process limitations industrial applications by taking
structure, in which each domain with reduce the potential applications of advantage of the high-speed oxide
an ideally ordered array of nanopores nanoporous alumina. Substantial efforts growth (50–100 μmh–1).56,57 However,
is separated with neighboring domains have been made to explore a new self- the process has not been employed in
by a boundary along which defect ordering regime in a wider range of current nanotechnology research due to
pores and imperfections in pore Dint.51–53 The research activity to date the difficulties involved in controlling
arrangement are present.18,44 For certain includes extending the voltage range by important structural parameters, such as
nanotechnology applications, it is pore size (Dp), interpore distance (Dint),
highly desirable to utilize long-range and the aspect ratio of the nanopores
ordered AAOs without any defects. of the resulting anodic alumina. By
Fabrication of ideally ordered AAO introducing a thin protective oxide
with a single-domain configuration over layer on aluminum prior to performing
a few mm2 area was first demonstrated HA process and carefully controlling
by Masuda et al. by anodizing a pre- the reaction heat during HA, Lee et al.
patterned aluminum.45 The process could suppress the burning event and
involves pre-texturing of the aluminum grow self-ordered AAOs using oxalic
surface by nanoindentation using an acid at anodization potentials U > 100
appropriate stamp prior to anodization V, establishing a new self-ordering
(see Figure 3). Each indent formed a regime with a widely tuneable interpore
on the aluminum substrate by nanoin- distance (Dint = 200–300 nm) (Figure
dentation initiates pore nucleation and 2f). The rate of oxide growth in HA
leads to a long-range ordered pore was found to be 25 to 35 times faster
arrangement within the stamped area. than that in MA. The newly developed
This method was further extended to method turned out to be applicable to
fabricate a hole array architecture with other electrolyte systems.8,59
square- or triangle-shaped openings The HA process is characterized by a
in a close-packed square or hexagonal high current density (j) that is typically
b
arrangement.46 Several groups have one or two orders of magnitude higher
Figure 4. (a) An SEM micrograph show-
achieved pre-patterning of aluminum ing a cross section of AAO fabricated by than that of the ordinary MA. The
by employing a focused ion beam (FIB) a combination of mild anodization (MA) current in anodization of aluminum is
technique,47 holographic lithography,48 and hard anodization. A magnified cross- related to the passage of ionic species
section image of the area marked with
and microsphere lithography,49 and a white rectangle is shown as an inset. through the barrier layer. Under high
demonstrated fabrication of single- Reprinted from Reference 55; (b) SEM field condition, the ionic current
domain AAOs with an arbitrary micrographs of AAOs that experienced density (j) can be related to the electric
spontaneous current oscillations during
interpore distance (Dint). An economic hard anodization. Oscillating current pro- field strength (E); j = joexp(βE) =
approach to the fabrication of single- files determine the internal pore geom- joexp(βΔU/tb), where jo and β are the
domain AAOs in a wafer-scale is also etries of nanoporous AAO. Reproduced material-dependent constants and ΔU/tb
from Reference 62 with permission ©
currently available.50 Wiley-VCH Verlag GmbH & Co. KGaA. is the effective electric field strength (E)
Nanoimprint-assisted anodization across the barrier layer of thickness tb.

60 www.tms.org/jom.html JOM • June 2010

Investigation of HA processes revealed that originated from the surface each anodized segment is determined
that the current density (i.e., the electric topography. by the pulse durations (τMA and τHA) at
field strength E across the barrier layer) given anodization potentials (UMA and
PULSE ANODIZATION
is a key parameter governing the self- UHA) (Figure 5c).
organization of oxide nanopores in a As mentioned in the previous An interesting finding from the case
given anodization potential (U). The section, combination of conventional of sulfuric acid-based PA is that an
barrier layer thickness for HA increases MA and the newly developed HA oxide segment (HA-AAO) formed by
at a rate of tbMA = 0.6–1.0 nmV–1,55,60 could offer a new degree of freedom a high potential pulse (UHA) contains a
which is smaller than tbMA ~ 1.2 nmV–1 for tailoring the pore structure of AAOs higher level of anionic impurity from
for MA processes.6,28 HA-AAOs by combining properties from the two the electrolyte than an oxide segment
exhibit a reduced voltage dependence anodization processes. Based on this (MA-AAO) formed by a low potential
of the interpore distance (Dint) with a pulse (UHA). Therefore, PA in sulfuric
proportionality constant ζHA = 1.8–2.0 The fabricated AAOs acid solution results in a periodic
nmV–1,55,58,59 compared to MA-AAOs compositional modulation along the
(i.e., ζMA = 2.5 nmV–1).21,24 Similar with modulated pore pore axes of AAO. HA-AAO segments
lines of experimental results have also structure could be with a higher impurity content exhibit
been reported by other researchers.52,61 a poor chemical stability against an
For oxalic acid-based HA, the poros- starting materials etchant (e.g., 5 wt.% H3PO4). This
ity (PHA) of HA-AAO turned out to be enables one to completely delaminate
PHA = 3.3–3.4%, which is about one-
for developing three- a single as-prepared anodic film into a
third of the porosity value (PMA ~ 10%) dimensional porous stack of well-defined AAO membranes
that was proposed as a requirement sheets by an extended etching of
for self-ordered AAO under MA con-
architectures that may HA-AAO segments (Figure 5d).
ditions.24 On the basis of the newly offer potential for Accordingly, PA followed by selective
found self-ordering behavior in HA, etching of HA-AAO segments by an
Lee et al. realized the fabrication of photonic applications, appropriate etchant provides a simple,
AAO membranes with periodically and also model systems continuous, and economic way for the
modulated diameter of nanopores along mass production of nanoporous AAO
the pore axes by combining MA and HA for investigating membranes.
process, in which each modulation step separations of particles PA can also be conducted under a
required the exchange of the electrolyte galvanostatic condition to tailor the
solution in order to satisfy both MA and and adsorption internal pore structure of AAO. In this
HA processing conditions (Figure 4a).55 characteristics of case periodic current pulses are applied
Quite recently, they further showed that to achieve MA and HA conditions,
AAOs experienced spontaneous current molecules. and anodization potential changes
oscillations (amplitude ~0.8 Acm–2) periodically to a value corresponding
during a potentiostatic HA can have concept, Lee et al. developed a generic to each pulsed current. Recently, Lee et
modulated pore structures, in which the approach for continuous structural al. reported a convenient method for the
modulation contrast is proportional to engineering of nanoporous AAO based preparation of structurally well-defined
the amplitude of current oscillation, and on pulse anodization (PA) of aluminum alumina nanotubes with controllable
suggested that one may achieve structural under a potentiostatic condition using lengths.64 The approach is based on the
engineering of nanoporous AAO by H2SO4 or H2C2O4.63 In a typical PA fact that H2SO4-AAO formed under a
deliberately manipulating the current process, periodic pulses consisting of high electric field strength (E) exhibits
during anodization of Al (Figure 4b).63 a low-potential pulse (UMA) followed a weakened junction strength between
The fabricated AAOs with by a high potential pulse (UHA) are cells. They employed galvanic pulses
modulated pore structure could be applied to continuously achieve MA to selectively combine MA and HA
starting materials for developing three- and HA conditions, respectively conditions, where the pulse duration
dimensional (3-D) porous architectures (Figure 5a). During PA in a given (τHA) for HA determines the length of
that may offer potential for photonic electrolyte, anodization current changes nanotubes. By taking advantage of the
applications, and also model systems periodically to a value corresponding weak junction strength between cells
for investigating separations of to each pulsed potential (i.e., jMA for and of the modulated pore structures
particles and adsorption characteristics UMA and jHA for UHA; jMA < jHA), and along the pore axis, individual alumina
of molecules. In addition, it is expected thus the pore structure of the resulting nanotubes could be separated from an
that these AAOs can be readily utilized AAO is periodically modulated (Figure as-prepared AAO.
as template materials for fabricating 5b). Nanoporous AAO formed by a The reaction involved in anodic oxi-
novel nanowires or nanotubes, whose PA process exhibits a layered structure dation of aluminum is exothermic. The
diameters are periodically modulated of MA-AAOs with a smaller pore dissolution of the resulting oxide by
along their axes, and thus, enable one diameter and HA-AAOs with a larger acid electrolyte is endothermic. The
to study the various physical properties pore diameter, in which the thickness of main contribution to heat generation in

Vol. 62 No. 6 • JOM www.tms.org/jom.html 61

 odization process. This generic process
allows continuous tailoring of the inter-
nal pore structure as well as the com-
Al position of the anodic oxide by delib-
erately designing the pulse sequences.
Pulse Anodization Therefore it provides a new degree of
(UHA, τHA) freedom in template-based synthesis of
(UMA, τMA)
functional nanostructures that can be
used for developing advanced devices
MA-AAO
HA-AAO
as well as for investigating a diverse
MA-AAO range of research problems in chemis-
HA-AAO
MA-AAO
try and physics.
HA-AAO In spite of some recent advances in
anodization of aluminum, there is still
much work to do. Exploration of new
electrolytes systems and novel porous
architectures will continue to expand
the field of applications of anodic
alumina. In addition, engineering the
properties (e.g., wear or plasma resis-
tance) of anodic films formed by the
new processes is an interesting subject
of research for the commercial appli-
cations. As mentioned in the present
Figure 5. (a) Scheme for the fabrication of AAO with modulated pore diameters by pulse overview, there are still many open
anodization. (b,c) SEM images showing the cross-sectional view of an as-prepared
AAO formed by H2SO4 pulse anodization. (d) SEM image of a stack of nanoporous AAO questions regarding the mechanism
membranes. All the MA-AAO segment slabs were delaminated from an as-prepared AAO responsible for the pore formation and
by selective removal of HA-AAO segments using an H3PO4. Reprinted from Reference 63. self-organization. Understanding the
electrochemical process during the an-
anodization of aluminum is related to odization of aluminum could provide a
CONCLUSION
current flow through the barrier oxide solid foundation for developing ordered
layer. The production of Joule’s heat Self-ordered porous alumina formed porous structures from other valve met-
(Q) is proportional to the square of the by anodization of aluminum has in- als, such as Hf, Ti, W, Zr, Nb, Ta, Sn,
current density (j) according to Q = Ujt creasingly become a popular template etc., which is currently an active area of
= Rbj2t, where Rb and t are the resistance system in the development of func- research.
of the barrier layer and the reaction tional nanostructures. Anodization of
ACKNOWLEDGEMENTS
time, respectively. HA is accompanied aluminum can be categorized into two
by a large evolution of heat due to the main groups; mild anodization and This article is dedicated to the mem-
high anodic current (j) associated with hard anodization. The former method ory of the late Prof. Ulirch Gösele.
the high electric field (E) at the barrier produces self-ordered and straight pore Financial support in part from the Ko-
oxide. Since current density (jHA) in HA structures, but it is slow and only works rea Research Council of Fundamental
is about one or two orders of magnitude for a narrow range of processing con- Science and Technology through the
higher than that (jMA) in MA, heat pro- ditions. The latter method, which is “Development of Advanced Industrial
duction during HA could be roughly widely used in the industry, is faster, Metrology” project is gratefully ac-
two to four orders of magnitude larger. but it produces anodic films with disor- knowledged.
The excessive heat does not only trig- dered and non-uniform pore structures.
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