Porous Anodic Aluminum Oxide: Anodization and Templated Synthesis of Functional Nanostructures

Review
pubs.acs.org/CR
Porous Anodic Aluminum Oxide: Anodization and Templated

Synthesis of Functional Nanostructures
Woo Lee*,†,‡ and Sang-Joon Park†
†
Korea Research Institute of Standards and Science (KRISS), Yuseong, 305-340 Daejeon, Korea
‡
Department of Nano Science, University of Science and Technology (UST), Yuseong, 305-333 Daejeon, Korea
6.2.3. Morphological Instability U
6.3. Steady-State Pore Formation W
6.3.1. Joule’s Heat-Induced Chemical Dissolu-
tion W
6.3.2. Field-Assisted Oxide Dissolution W
6.3.3. Average Field Model for Steady-State
Pore Structure X
6.3.4. Direct Cation Ejection Mechanism Y
6.3.5. Flow Model for Steady-State Pore
Formation Z
7. Self-Ordered Porous Anodic Aluminum Oxide
(AAO) AA
7.1. Mild Anodization (MA) AB
7.2. Hard Anodization (HA) AD
CONTENTS 7.3. Pulse Anodization (PA) AF
1. Introduction A 7.4. Cyclic Anodization (CA) AI
2. Types of Anodic Aluminum Oxide (AAO) B 7.5. Anodization of Thin Aluminum Films De-
3. Ionic Conduction in Anodic Oxide Films D posited on Substrates AI
3.1. High-Field Conduction Theory D 8. Long-Range Ordered Porous AAO AL
3.2. Elementary Interfacial Reactions D 9. AAO Template-Based Synthesis of Functional
3.3. Transport Numbers E Nanostructures AP
3.4. Stress-Driven Ionic Transport F 9.1. Electrochemical Deposition (ECD) AP
4. Electrolytic Breakdown G 9.2. Electroless Deposition (ELD) AS
4.1. Factors Influencing Breakdown G 9.3. Sol−Gel Deposition AS
4.1.1. The Nature of Anodized Metal H 9.4. Surface Modification AU
4.1.2. Electrolyte Conditions H 9.5. Template Wetting AZ
4.1.3. Current Density (j) H 9.6. Mask Techniques BA
4.1.4. Other Factors Influencing Breakdown H 9.7. Chemical Vapor Deposition (CVD) BB
4.2. Models for Breakdown I 9.8. Atomic Layer Deposition (ALD) BC
4.2.1. Electron Avalanche Multiplication I 10. Closing Remarks and Outlook BE
4.2.2. Stress-Driven Breakdown J Author Information BF
5. Structure of Porous Anodic Aluminum Oxide Corresponding Author BF
(AAO) K Notes BF
5.1. General Structure K Biographies BG
5.1.1. Pore Diameter (Dp) K Acknowledgments BG
5.1.2. Interpore Distance (Dint) M Abbreviations BG
5.1.3. Barrier Layer Thickness (tb) M References BI
5.2. Structure of Pore Wall (Anion Incorporation) M
5.3. Effect of Heat Treatments P
6. Growth of Porous Anodic Aluminum Oxide (AAO) P 1. INTRODUCTION
6.1. Stress Generation in Anodic Oxide Films P In ambient atmospheres, aluminum becomes rapidly coated
6.1.1. Volume Expansion P with a compact 2−3 nm thick oxide layer. This native oxide
6.1.2. Stress Measurements Q layer prevents the metal surface from further oxidation. Because
6.1.3. Effects of External Stresses on Pore of the surface native oxide, aluminum generally has good
Growth S corrosion resistance. However, local corrosion of metal can
6.2. Initial-Stage Pore Formation T occur in rather aggressive outdoor environments, containing
6.2.1. Qualitative Description on Pore Forma-
tion T
Received: January 2, 2014
6.2.2. Kinetics of Porosity Initiation T
© XXXX American Chemical Society A dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews Review
corrosive chemicals (e.g., chlorides or sulfates). In 1857, Buff discussed (section 5). Anodization of aluminum is a volume
first found that aluminum can be electrochemically oxidized in expansion process, and thus is accompanied by mechanical
an aqueous solution to form an oxide layer that is thicker than stresses. Recent studies have indicated that the stresses have
the native one.1 This phenomenon has been called “anodiza- profound implications not only on the ionic transport, but also
tion” because the aluminum part to be processed constitutes on the self-ordering behavior of oxide nanopores. We will
the anode in an electrolytic cell. In the early 1920s, the discuss in detail the effect of stress on pore growth (section
phenomenon observed by Buff was exploited for industrial scale 6.1), the kinetics of pore initiation, and morphological
applications, for example, protection of seaplane parts from instability associated with the early stage of anodization
corrosive seawater.2 In general, the anodic aluminum oxide (section 6.2), and recent models describing steady-state pore
(AAO) films form with two different morphologies (i.e., formation (section 6.3). After that, recent progress on
nonporous barrier-type oxide films and porous-type oxide anodization of aluminum used in fabricating self-ordered
films) depending mainly on the nature of the anodizing porous AAO and also for engineering internal pore structures
electrolyte.3 Because the process was first implemented for will be discussed (section 7). In addition, various approaches to
protection purposes, the anodization of aluminum and its long-range order porous AAO will be reviewed (section 8). In
alloys, particularly porous-type anodization, has received the last part of this Review (section 9), various chemical
considerable attention in the industry because of its extensive approaches for the syntheses of low-dimensional functional
practical applications. Many desirable engineering properties nanostructures and the fabrications of advanced nanodevices
such as excellent hardness, corrosion, and abrasion resistance will be discussed. These approaches include electrochemical
can be obtained by anodizing aluminum metals in acid deposition (ECD), electroless deposition (ELD), sol−gel
electrolytes.4 In addition, due to its high porosity, the porous deposition, surface modification, template wetting, shadow
oxide films formed on the metals serve as a good adhesion base mask techniques, chemical vapor deposition (CVD), and
for electroplating, painting, and semi-permanent decorative atomic layer deposition (ALD). Chemistry issues encountered
coloration. The anodized products can be easily found in in the template-based synthesis of functional nanostructures
electronic gadgets, electrolytic capacitors, cookware, outdoor will be discussed in detail. Finally, we will present the
products, plasma equipment, vehicles, architectural materials, challenges and future prospects of the field (section 10).
machine parts, etc. Recently, this nearly century-old industrial
process has been drawing increasing attention from scientists in 2. TYPES OF ANODIC ALUMINUM OXIDE (AAO)
the field of nanotechnology. This trend originated with the Anodization of aluminum in aqueous electrolytes forms anodic
seminal works of Masuda and co-workers, who reported on oxide films with two different morphologies, that is, the
self-ordered porous AAO in 19955 and the subsequent nonporous barrier-type oxide films and the porous-type oxide
development of the two-step anodization process in 1996.6 films. The chemical nature of the electrolytes mainly
Porous AAO film grown on aluminum is composed of a thin determines the morphology of AAOs.3,7,8 A compact non-
barrier oxide layer in conformal contact with aluminum, and an porous barrier-type AAO films can be formed in neutral
overlying, relatively thick, porous oxide film containing electrolytes (pH 5−7), such as borate, oxalate, citrate,
mutually parallel nanopores extending from the barrier oxide phosphate, adipate, tungstate solution, etc., in which the anodic
layer to the film surface.7 Each cylindrical nanopore and its oxide is practically insoluble.9,10 Meanwhile, porous-type AAOs
surrounding oxide region constitute a hexagonal cell aligned are formed in acidic electrolytes, such as selenic,11 sulfuric,12
normal to the metal surface. Under specific electrochemical oxalic,12 phosphoric,7,12,13 chromic,12,14 malonic,12,15−17 tarta-
conditions, the oxide cells self-organize into hexagonal close- ric,12,18 citric,12,17−20 malic acid,12,18 etc., in which anodic oxide
packed arrangement, forming a honeycomb-like structure.5−7 is slightly soluble. Early models describing anodic oxide growth
Pore diameter and density of self-ordered porous AAOs are were developed on the basis of the barrier-type oxide.21−24
tunable in wide ranges by properly choosing anodization Moreover, in the early stage of porous-type oxide growth, the
conditions: pore diameter = 10−400 nm and pore density = formation of the initial barrier oxide is followed by the
108−1010 pores cm−2. The novel and tunable structural features emergence of incipient pores. Therefore, in this Review, we will
of porous AAOs have been intensively exploited for synthesiz- mention the barrier-type oxide growth to the extent needed for
ing a diverse range of nanostructured materials in the forms of understanding porous-type oxide formation. Some excellent
nanodots, nanowires, and nanotubes, and also for developing review articles covering the barrier-type anodic oxide films are
functional nanodevices. given in refs 3 and 25.
The objective of this Review is to provide a solid information The two types of anodic oxides (i.e., barrier- vs porous-type
source for researchers entering this field and to establish a AAO) differ in their oxide growth kinetics. In the case of
broad and deep knowledge base. This Review introduces the barrier-type oxide formation under potentiostatic conditions
fundamental electrochemical processes associated with anodic (i.e., U = constant), current density (j) decreases exponentially
oxidation of aluminum, and discusses the recent progress on with time (t). Correspondingly, the film growth rate decreases
anodization of aluminum for the development of ordered almost exponentially with time (t), which places a limit on the
porous AAOs, and nanotechnology applications of porous maximum film thickness obtainable for barrier-type AAO films
AAOs. We organize this Review as follows: after discussing the (Figure 1). It has been experimentally verified that the
growth characteristics of two different types of AAOs (section thickness of barrier-type film is directly proportional to the
2), we will describe the theory of ionic conductions and applied potential (U). On the other hand, current density (j) in
elementary interfacial reactions (section 3), followed by porous-type anodization under potentiostatic conditions
electrolytic breakdown (section 4) to understand the remains almost constant within a certain range of values during
fundamental electrochemistry associated with anodic oxidation the anodization process, due to the constant thickness of the
of aluminum. Next, the electrochemical factors defining the barrier layer at the pore bottom. The thickness of the resulting
geometric and chemical structures of porous AAOs will be porous oxide film is linearly proportional to the total amount of
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aluminum, new oxide forms above and below the marker

layer (Figure 2b). The marker layer is located at a depth of 40%
of the film thickness in a plane corresponding to that of the
original metal surface. On the other hand, when a barrier-type
film is formed at 60% current efficiency (ηj), the plane of the
marker layer is immobile and 40% of the Al3+ cations are shed
into the electrolyte via direct cation ejection mechanism
without contributing to the oxide formation (Figure 2c). In this
case, anodic oxide grows at the metal/oxide interface via the
inward migration of O2−/OH− ions. When porous-type anodic
oxide forms at 60% current efficiency, the marker plane is
located above that of the original metal surface (Figure 2d). In
this case, the metal/oxide interface is also the oxide growth
front, and 40% of Al3+ ions are ejected into the solution.
Because cations are being shed into the electrolyte, the
current efficiency (ηj) of porous-type oxide growth is typically
much lower than that of the barrier-type. Accordingly, the
Pilling−Bedworth ratio (PBR = the ratio of molar volume of
the grown oxide to molar volume of the consumed metal; see
Figure 1. Two different types of anodic aluminum oxide (AAO) section 6.1.1) for the initial barrier oxide formation in porous-
formed by (a) barrier-type and (b) porous-type anodizations, along type oxide growth at the early stage of anodization is lower than
with the respective current (j)−time (t) transients under potentiostatic that for barrier-type oxide growth: PBR = 0.90 for porous-type
conditions.
oxide growth at ηj = 53.5% in phosphoric acid solution and
PBR = 1.7 for barrier-type oxide growth at ηj = 100% in neutral
charge (i.e., anodization time, t) involved in the electrochemical
adipate solution.9,33 Shimizu et al.33 suggested that the initial
reaction.
Radiotracer studies, employing an immobile marker (125Xe), barrier oxide grows under increasing tensile stress (PBR < 1),
have indicated that, in the case of barrier-type oxide formation, which causes local oxide cracking most probably at the
anodic alumina grows simultaneously at the oxide/electrolyte randomly present metal protrusions. The generated surface
interface and at the metal/oxide interface, through Al3+ egress cracks were considered to be local paths for electrolyte
and O2−/OH− ingress, respectively, under a high electric field penetration, causing non-uniform local thickening of the initial
(E).26−28 In the case of porous-type anodic alumina formation, barrier oxide. Non-uniform thickening of the initial oxide causes
on the other hand, oxide grows at the metal/oxide interface via concentration and redistribution of the current lines into the
the inward migration of O2−/OH− ions. 18O tracer studies have relatively thin oxide regions between the protrusions (i.e., a
shown that outwardly migrating Al3+ cations do not contribute local increase in electric field, E). Consequently, localized
to the oxide growth at the oxide/electrolyte interface, but are all scalloping of the metal/oxide interface takes place. Shimizu et
shed into the anodizing electrolyte via direct ejection al.33 pointed out that the non-uniform thickening of anodic
mechanism (see section 6.3.4).10,29−31 Otherwise, egressing oxide (i.e., morphological instability) in the initial barrier oxide
Al3+ ions would form anodic alumina at the oxide/electrolyte is “one of the most distinctly different growth features between
interface to heal any developing or embryonic pores there. porous- and barrier-type AAO films”. Unlike porous-type oxide
Schematic diagrams illustrating the dimensional changes of growth in acid electrolytes, anodic oxides in neutral electrolytes
aluminum during the barrier-type and porous-type anodic oxide grow highly uniformly on surface finished aluminum,
formation are shown in Figure 2.32 An immobile marker layer is maintaining flat metal/oxide and oxide/electrolyte interfaces.
implanted into the starting aluminum with a native oxide layer Even the smoothing of initially rough aluminum surfaces during
(Figure 2a). When a barrier-type film is formed at 100% current the growth of barrier oxide films has been experimentally
efficiency (ηj) by anodization of the marker-implanted observed.34
Figure 2. Schematic diagrams illustrating dimensional changes of an aluminum specimen following anodizing. (a) Initial aluminum with a thin air-
formed oxide film. The red dashed line represents an immobile marker layer implanted into the initial aluminum with a thin air-formed oxide film.
(b) Anodized at 100% efficiency with formation of a barrier-type anodic film. (c) Anodized at just above 60% efficiency with formation of a barrier-
type anodic film. (d) Anodized at 60% efficiency with formation of a porous anodic film. Reproduced with permission from ref 32. Copyright 2006
The Electrochemical Society.
C dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

3. IONIC CONDUCTION IN ANODIC OXIDE FILMS in the oxide is high enough (e.g., 106−107 V cm−1), the ionic
current density (j) can be expressed as25
3.1. High-Field Conduction Theory
⎛ W ⎞⎛ αazFE ⎞
When a valve-metal is anodized under either potentiostatic or j = vρa exp⎜ − ⎟⎜ ⎟
⎝ RT ⎠⎝ RT ⎠ (2)
galvanostatic condition, anodic oxide film forms on the metal.
For anodizing aluminum (Al) and tantalum (Ta), an empirical where v is the hopping attempt frequency of the ion, ρ is the
exponential dependence of the ionic current density (j) on the density of concentration of mobile charge in C cm−3, a is the
electric field (E) is established. Ionic current density (j) under hopping inter-distance, W is the hopping activation energy at
high-field conditions, which is the case for anodic oxide growth, zero field, α is a parameter describing the asymmetry of the
can be associated with the movement of charged ions in the activation barrier at non-zero field, z is the valence of the
barrier oxide, and can be related to the potential drop (ΔU) mobile ions, and F is Faraday’s constant. From eqs 1 and 2, the
across the barrier oxide through the exponential law of following relations can be obtained:
Güntherschulze and Betz, as follows:21,35 ⎛ W ⎞
j0 = υρa exp⎜ − ⎟
j = j0 exp(βE) = j0 exp(β ΔU /tb) ⎝ RT ⎠ (3)
(1)
αazF
where j0 and β are material-dependent constants at a given β=
(4)
temperature, and ΔU/tb is the effective electric field (E, RT
typically 106−107 V cm−1) impressed on the barrier layer with Because the parameter a can be related to the inter-atomic
thickness tb. For anodic alumina, a large range of j0 and β values distance in the oxide, one can expect that the electric field
has been reported: j0 = 3 × 104 to 1 × 10−18 A cm−2 and β = 0.1 strength (E) increases when the oxygen ion density increases
× 10−6 to 5.1 × 10−6 cm V−1.25 (i.e., a decrease in parameter a) provided that the other
For anodic oxidation of metal in an electrolyte, three theories parameters are constant. Equation 1 can be modified to obtain
based on the following possible rate-determining steps for oxide a Tafel equation:
formation have been developed:3 ion transfers (i) across the ln j = ln j0 + βE (5)
metal/oxide interface (Mott−Cabrera theory),23,24 (ii) through
the oxide bulk (Verwey theory),22 and (iii) across the oxide/ For a constant oxide thickness tb, a constant Tafel slope β is
electrolyte interface (Dewald theory).36,37 In the point defect obtained.
model of Macdonald et al.,38 the oxide film is assumed to The electric field (E) in the oxide can be related to the
contain a high concentration of non-interacting positive and applied (or measured, in the potentiostatic condition) electrode
negative point defects, and the rate-determining step for the potential (U). The measurable potential drop between the
oxide growth is assumed to be the transport of metal and oxide metal and the electrolyte is equal to
vacancies across the oxide film. All of these theories can explain
U = ΔU + Φm/o + Φo/e (6)
the empirical exponential relationship proposed by Günter-
shultz and Betz. On the other hand, transient experiments where ΔU is the potential drop in the oxide, and Φm/o and Φo/e
favorably indicate that the rate-determining step is the are the potential drops at the metal/oxide and oxide/electrolyte
movement of charged ions within the oxide.25 interfaces, respectively.39 In a typical anodization, the potential
On the basis of the rate-determining movement of ions drops at the metal/oxide and oxide/electrolyte interfaces are
within the oxide, the high-field model relates the parameters j0 quite small, as compared to the several tens of volts of potential
and β in eq 1 to the nature of oxide materials. The high-field drop in the oxide (i.e., ΔU ≫ Φm/o + Φo/e). Therefore, the
conduction model is based on a hopping mechanism, in which following approximation for the electric field (E) is possible for
the activation energy for hopping ions is dependent on electric the high-field ionic transport:
field E (Figure 3).25 Ions at regular sites or interstitial positions
E = ΔU /tb ≈ U /tb (7)
jump to vacancies or other interstitial positions in their
neighborhood. The model assumes that the oxide is defect-free where tb is the thickness of oxide.
and of homogeneous composition. When the electric field (E) 3.2. Elementary Interfacial Reactions
As was already discussed in section 2, it is now widely accepted
that for the anodic growth of alumina both Al3+ cations and
oxygen-containing anions (e.g., O2− or OH−) are mobile within
the anodic oxide under high electric field (E).10,26−28,40 Al3+
ions migrate outwardly toward the oxide/electrolyte interface,
while O2− or OH− anions move inwardly toward the metal/
oxide interface. Therefore, one can consider both (i) the metal/
oxide and (ii) the oxide/electrolyte interfaces as the growth
front of anodic oxide during anodization of a valve-metal. For
anodizing aluminum, the following elementary reactions are
considered to be possibly occurring at the interfaces (Figure 4).
(i) At the metal/oxide interface:
3+
Al → Al(ox) + 3e− (8)
Figure 3. Influence of the electric field strength (E) on the activation
energy of hopping ions. Reproduced with permission from ref 25. 3+ 2−
Copyright 1993 Elsevier.
2Al(ox) + 3O(ox) → Al 2O3 (9)
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Figure 4. Schematic diagrams showing elementary interfacial reactions for (a) barrier-type and (b) porous-type anodic oxide.
(ii) At the oxide/electrolyte interface: and t− = 1 − t+ for anion. Transport numbers can be
3+ 2− determined by employing a “marker layer”, whose position in
2Al(ox) + 3O(ox) → Al 2O3 (10) the anodic oxide film indicates the extent of oxide that was
+ 3+
formed at each interface. If the metal ions are the only mobile
Al 2O3 + 6H(aq) → 2Al(aq) + 3H 2O(1) (11) species, new oxide should be formed at the oxide/electrolyte
interface on top of the marker layer. On the other hand, if
3+ 3+
Al(ox) → Al(aq) (12) oxygen anions are the only mobile species, the new oxide
should be formed at the metal/oxide interface below the
2−
2O(ox) + O2(g) + 4e− (13) marker layer. Davies et al.26 stated that the ideal marker atoms
for determination of transport numbers should fulfill the
2−
2H 2O(1) + O(ox) −
+ OH(ox) +
+ 3H(aq) (14) following requirements: “The markers should be (i) uncharged,
so that they do not migrate in the oxide under the influence of
Reactions 9 and 10 correspond to the formation of anodic the applied field; (ii) large in size, so that they do not diffuse
oxide at the metal/oxide and oxide/electrolyte interfaces, significantly within the oxide lattice; (iii) present in trace
respectively. Reaction 11 describes dissolution of anodic amount, so that the macroscopic properties of the tagged oxide
alumina by Joule’s heat-induced oxide dissolution and/or remain unaltered; and (iv) detectable, in order to assess their
field-induced oxide dissolution, which will be discussed in depth in the oxide.”
section 6.3.1 and section 6.3.2, respectively. On the other hand, These conditions can be satisfied by implanting radioisotopes
reaction 12 occurs through field-assisted direct ejection of Al3+ 125
Xe inert gas atoms or 222Rn, which are heavier than typical
ions from the metal/oxide interface through oxide into the valve-metals and oxygen, in a preformed thin oxide film and
electrolyte, which will be discussed in detail in section 6.3.4. subsequently anodized.26,27,42 Radioactive tracers allow the
Reactions 11−13 decrease the net current efficiency (ηj) position of the buried marker to be assessed by monitoring the
associated with the anodic oxide formation. Reaction 14 energy of emitted α- or β-particles.26,27,42,43 Other techniques
describes the heterolytic dissociation of water molecules at the to measure the buried marker position in oxide include
oxide/electrolyte interface, which supplies oxygen anions to the Rutherford backscattering spectrometry (RBS)40 or direct
metal/oxide interface to form anodic oxide. By assuming that observation of voids formed by implanted Xe by employing
all oxide anions from the dissolution of Al2O3 at the oxide/ cross-sectional transmission electron microscopy (TEM).28,44 A
electrolyte interface migrate to the metal/oxide interface to
representative cross-sectional TEM image showing an immobile
reform Al2O3, and that all oxide anions from the dissociation of
Xe marker layer is given in Figure 5. The sample in the figure
water contribute to the oxide formation, Su et al. proposed the
was formed in near-neutral potassium phosphate electrolyte at a
following overall reaction at the oxide/electrolyte interface:41
high current efficiency (ηj ≈ 100%).44 The approximately 10-
3+ 2− nm-thick straight Xe marker layer is located at about the
Al 2O3 + nH 2O(1) → 2Al(aq) + (3 − n − x)O(ox)
midpoint of the film. The anodic oxide above the marker layer
− +
+ xOH(ox) + (2n − x)3H(aq) (15) formed by the field-driven outward migration of Al3+ ions and
that beneath the marker layer by the field-driven inward
where n denotes the amount of water dissociated per mole of migration of oxygen carrying anions, O2−/OH−. Assuming that
Al2O3 that is dissolved at the same time. Su et al. claimed the all egressing Al3+ ions contribute to the oxide formation, the
field-dependent nature of the heterolytic dissociation of water cation transport number was directly estimated to be t+ =
in reaction 14 and related the dissociation rate of water to the 0.49.44 For anodizing conditions under which oxide grows with
porosity (P) of AAO, which will be touched upon in section appreciable metal dissolution, however, TEM-based direct
7.1. measurement may underestimate the cation transport number.
3.3. Transport Numbers In such cases, Al3+ ions dissolved in anodizing electrolyte
As mentioned in previous sections, anodic oxide formation can should be quantified to estimate the equivalent oxide thickness.
occur at both the metal/oxide and the oxide/metal interfaces. Davies et al.26 pointed out that the location of an immobile
The relative amount of mobile ions transported to the oxide marker in anodic oxide markedly depends on the anodization
forming interfaces is called the “transport number”: t+ for cation conditions, such as current density (j) and the nature of
E dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
Figure 5. Cross-sectional transmission electron microscopy (TEM)

image showing immobile 125Xe marker layer. The sample (i.e., barrier-
type anodic oxide film) was formed at a constant current density of 1
mA cm−2 to 100 V in near-neutral potassium phosphate electrolyte. Figure 6. Schematics showing (a) the movement of Al3+ and O2− ions
Adapted from ref 44 with permission. Copyright 1987 Taylor & during the re-anodizing process and (b) the corresponding cell
Francis (www.tandfonline.com). potential (U)−time (t) curve. Reproduced with permission from ref
46. Copyright 1978 Elsevier.
electrolyte. The authors performed transport number experi- ⎡ dh+ dh− ⎤ jM
ments using radioisotope 125Xe marker atoms and also ρ ⎢P + ⎥=
quantitative analyses on dissolving Al3+ ions during anodization ⎣ dt dt ⎦ nFk (16)
in two different near-neutral electrolytes (i.e., sodium −3
where ρ (=2.95 g cm ) is the density of oxide, P is the porosity
tetraborate and ammonium citrate). According to their
of porous AAO, dh+/dt and dh‑/dt are, respectively, the rates of
experiments, both metal and oxygen ions are mobile during
the increase of the barrier oxide thickness at the oxide/
oxide growth. In the borate solution, anodic alumina grew with
electrolyte and metal/oxide interfaces, j is the current density,
high current efficiencies (i.e., negligible cation loss), and thus
M is the atomic weight of Al, n (=3) is the number of electrons
the immobile 125Xe markers were completely buried in the
involved in oxidation reaction, F is Faraday’s constant, and k
oxide. The mean cation transport number (t+) was estimated to
(=0.505) is the weight fraction of aluminum in the oxide. The
be t+ = 0.58 for anodic alumina formed at the current density
cation transport number is given by the ratio of the weight of
range of 0.1−10 mA cm−2. On the other hand, in citrate
new oxide formed within the pores per unit time to the total
solution, the amount of aluminum passed into the solution was
weight of new oxide formed per unit time:46
as high as 40% of the total oxidized metal at low current
density, but decreased as the current density increased. The ⎛ dh+ ⎞ ⎛ dh+ dh− ⎞
125
Xe markers in anodic alumina remained very close to the t + = ⎜P ⎟ / ⎜P + ⎟
⎝ dt ⎠ ⎝ dt dt ⎠ (17)
outer surface. The cation transport number varied with current
density, from about t+ = 0.37 at 0.1 mA cm−2 to t+ = 0.72 at 10 The slopes m1 and m2 of the U−t transient in Figure 6b are
mA cm−2. given by46
In the case of porous AAO, the transport numbers of mobile
ions can be estimated by the so-called “pore-filling method”, 1 ⎛ dh+ dh− ⎞
m1 = ⎜ + ⎟
which was originally used to determine the porosity (P) of AR ⎝ dt dt ⎠ (18)
porous AAO by Dekker and Diddelhoek.45,46 In this method,
aluminum is first anodized in an acid electrolyte to form 1 ⎛ dh+ dh− ⎞
porous-type anodic oxide and subsequently re-anodized in a m2 = ⎜P + ⎟
AR ⎝ dt dt ⎠ (19)
neutral electrolyte electrolyte to form barrier-type oxide under a
galvanostatic condition. During anodizations, potential (U)− where AR is the anodizing ratio (=the ratio of the barrier layer
time (t) transients are monitored. During the barrier-type thickness to the cell potential, in nm V−1), and assumed to be a
anodizing (i.e., re-anodizing process), new oxide gradually constant. From eqs 16−19, the porosity (P) of porous AAO is
forms simultaneously within the pores and underneath the given by
barrier layer of the pre-formed porous anodic oxide, because
both Al3+ and O2− ions contribute to the oxide formation at the t +(m2 /m1)
P=
metal/oxide and oxide/electrolyte interfaces, respectively. As a 1 − (1 − t +)(m2 /m1) (20)
result, the cell potential gradually increases with time during the
For porous AAO formed in 1.125 M oxalic acid at 30 V,
re-anodizing process. Figure 6 schematically shows (a) the
Takahashi and Nagayama reported that the transport numbers
movement of Al3+ and O2− and (b) the cell potential (U)−time
of mobile Al3+ and O2− ions are t+ = 0.4 and t− = 0.6,
(t) profile during the re-anodizing process.46 The non-zero
respectively.46
value of U at t = 0 is due to the original barrier layer of pre-
formed porous AAO. The complete filling of pores is 3.4. Stress-Driven Ionic Transport
accompanied by the change of the slope in the U−t curve at The high-field conduction model describes the relation
time tp due to the sudden increase of the oxide/electrolyte between ionic current density (j) and the electric field (E)
interfacial area. For the time t < tp, the following relation can be well. However, stress gradients in the oxide may possibly
obtained:46 contribute to the ionic transport. Hebert and Houser47,48 have
F dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
developed a model for ionic transport in growing amorphous to tensile transition at 0.5−1.0 mA cm−2), while average tensile
anodic alumina films, in which ion migration in the oxide is stress of the order of 50 MPa was predicted above 1 mA cm−2,
driven by gradients of mechanical stress as well as electric which is in good agreement with the experimental stress data of
potential. It also considers the viscoelastic creep of the oxide. In Bradhurst and Leach.50 In addition, by taking into consid-
other words, both stress gradient-driven ionic migration and eration the viscous flow of oxide material, the model predicted
stress gradient-driven creep are considered in the model. It is the increases of the cation transport number (t+) as a function
assumed that stress originates at the metal/oxide interface due of current density (j). On the basis of experimental evidence
to the volume change upon oxidation. For stress gradient- that cation transport number (t+) is largely dependent on the
driven ionic migration, the empirical high-field conduction electrolyte condition, Hebert and Houser pointed out that the
relation is generalized by considering the dependence of the oxide viscosity and conduction parameters may depend on the
ionic current density on the gradient of the ionic chemical solution composition as a result of electrolyte anion
potential ∇μi:47−49 incorporation into the anodic oxide film. They suggested that
bulky electrolyte anions disrupt the local packing of oxygen
∇μi ⎛ a ⎞
Ji = −2 C iu i0 sinh⎜ |∇μi |⎟ ions and influence transport properties by the introduction of
|∇μi | ⎝ RT ⎠ (21) additional free volume into the amorphous oxide.48
where Ji, Ci, and are, respectively, the flux, the concentration,
u0i
and the pre-exponential velocity of ion “i” (i = M and O for 4. ELECTROLYTIC BREAKDOWN
metal and oxygen, respectively), and a is the migration jump When valve-metals (e.g., Al, Ta, Nb, Zr, etc.) are anodized
distance in the oxide. The chemical potential μ is related to the under galvanostatic conditions, the thickness of the oxide films
mean stress (σ) and electrical potential (ϕ) as follows:48 increases linearly with time. Correspondingly, the applied
potential (U) increases linearly with time to keep the electric
μi = u i0 + z iFϕ − Vi̅ σ (22) field (E) constant during the process. Under this condition, the
where zi, and V̅ i are the standard chemical potential, the
u0i , anodizing potential (U) finally reaches a value at which visible
charge number, and the molar volume of ion i, respectively. For sparking on the anode starts appearing, and local thickening,
barrier-type anodic alumina film, the mean normal stress is cracking, blistering, or even burning of oxide film commences.
defined according to σ = 1/3(σxx + σyy) = 2/3σxx, where x- and This local event is called “electrolytic breakdown”, which not
y-directions are parallel to the interface.47 For the stress only prevents the uniform growth of anodic films over the
gradient-driven oxide creep, the model enforces the con- macroscopic metal surface, but also permanently degrades the
servation of electrical charge and volume and the momentum dielectric properties of the oxide. The anodizing potential at the
balance in a Newtonian fluid. For galvanostatic anodization of onset of this local event is called breakdown potential (UB).
aluminum at the applied current density j, the constraint of Because the oxide thickness increases linearly with the
charge conservation can be written as follows: anodizing potential (U) in galvanostatic conditions, the
breakdown is dependent on the oxide thickness and occurs at
j = −2FJO + 3FJM (23) a critical oxide thickness. Breakdown during anodization can be
On the other hand, the volume balance is associated with a number of phenomena. These include the
appearance of visible sparking/luminescence,51−59 the local
jΩM crystallization of oxide, 60−66 oxygen evolution at the
= −VO̅ JO − v
3F (24) anode,63,67,68 retardation of potential rise,69,70 occurrence of
audible cracking,71 and rapid voltage fluctuations.69,70,72 In
where ΩM is the molar volume of the Al atom in the metal and
porous AAO growth, breakdown can occur under high current
v is the creep velocity in the oxide. By employing the Maxwell
density anodizing conditions.4 If the reaction heat cannot be
viscoelastic model and also by assuming a large elastic modulus,
adequately dissipated from the anode, electrolyte heating may
the momentum balance in a Newtonian fluid is expressed as47
cause local increase in conductivity and a current “run away”
1 1 process. This results in local thickening or burning of anodic
0= ∇σ + ∇2 v + ∇(∇·v)
η 3 (25) oxide, terminating uniform growth of porous AAO. The anodic
oxide in the burnt area exhibits typically a different color from
where η is the viscosity. the burnt-free areas. For a given anodizing electrolyte, on the
For porous AAO film growing under steady-state,47 the other hand, porous AAO formed at a potential just below
model predicted that a large compressive interfacial stress breakdown value (i.e., U < UB) exhibits the best self-ordering of
causes the lateral flow of oxide materials from the center of pores (section 7.1).18 Improving the breakdown characteristics
pore base toward the cell boundaries and the upward flow in of anodic oxide films through proper control of the electrolyte
the pore wall oxide, as in the flow pattern experimentally composition, surface state of the starting aluminum, and
observed from W tracer studies (see section 6.3.5). Simulation reaction heat can allow one not only to explore new anodizing
results indicated that the stress field driving the flow results conditions for self-ordered pore growth, but also to engineer
from the following three origins: “the volume expansion internal pore structures (see sections 7.2−7.4). In this section,
occurring at the metal/oxide interface, nonlinearity of the we discuss some of the electrochemical factors influencing
equations governing conduction of mobile ions (i.e., Al3+ and breakdown, and models that explain the breakdown phenom-
O2−/OH−), and incorporation of electrolyte-derived anionic ena.
species within the anodic oxide near the oxide/electrolyte
interface”.47 4.1. Factors Influencing Breakdown
For barrier-type anodic alumina film,48 the model predicted In general, the breakdown potential (UB) is dependent on the
the average stress in the oxide to be compressive when the nature of the metal being anodized, the current density (j), and
current density is smaller than 0.5 mA cm−2 (i.e., compressive the composition (or resistivity) of the electrolyte. Meanwhile,
G dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
the electrolyte temperature, stirring rate, and history of anodic film. For anodic oxide of aluminum, some authors have
oxide have no influence on the breakdown potential. reported that anion concentration (CA−) influences UB.76,77
4.1.1. The Nature of Anodized Metal. Wood and Kato et al. showed that at a fixed solution resistivity UB
Pearson investigated metals whose anodization in 3% decreases linearly with an increase in the logarithm of the
ammonium tartrate ended in sparking, and associated the anion concentration, or more specifically the anion charge with
breakdown potential (UB) with the ionic bonding character- the following relation:77
istics of the anodic oxides by employing the criteria of Pauling
UB = A − B log C A− (27)
and Wells. They established a descending order of UB according
to the melting point of the corresponding oxide: Zr (300 V) > On the basis of anodization experiments with tantalum in
Al (245 V) > Ta (200 V) > Nb (190 V).72 However, Alwitt and sulfuric, phosphoric, and hydrochloric acids, Arifuku et al.78
Vijh reported a different descending order of UB for reported that UB is dependent upon the detailed distribution
anodizations of the same metals in the same conditions: Al profiles of incorporated anions in the anodic oxide. Later, the
(350 V) > Zr (315 V) > Ta (275) > Nb (190 V).73 They role of incorporated electrolyte species in the electrical
correlated the increase in UB with the increasing heat of breakdown was emphasized by Albella et al., who have put
formation per equivalent (−ΔHf/equiv) of oxide, which is forward a theory of avalanche breakdown during anodic
approximately equal to one-half the value of the forbidden band oxidation.79−81
gap of the oxide. Further, they noted that the dependence of UB 4.1.3. Current Density (j). For tantalum anodization in
on the band gap would reflect the electronic nature of the ammonium sulfate, Yahalom and co-workers76,82 reported that
breakdown phenomena. As such, rather conflicting reports have the breakdown potential (UB) is almost independent of the
been published for the dependence of UB on the intrinsic solid- current density (j). For anodic films on aluminum, Ikonopisov
state properties of anodic oxides. Iknopisov et al.69 pointed out et al.69 also reported that a 500-fold increase of current density
that the dependence of UB on the nature of the metal is (j) only lowers the breakdown potential (UB) by 15%. On the
considerably smaller than the dependence on the electrolyte other hand, Di Quarto et al.74,75,83 pointed out the occurrence
resistivity (ρe). of two different kinds of breakdown, that is, “mechanical” and
4.1.2. Electrolyte Conditions. Early studies have reported “electrical” breakdown. For anodic oxides of tungsten,74
that the breakdown potential (UB) increases linearly with the zirconium,75 and titanium84,85 under limited conditions, they
logarithm of the electrolyte resistivity (ρe) with the following noted that anodic oxides grew with an increasing number of
equation: defects at a retarded rate (i.e., reduced slope in U−t curve)
during galvanostatic anodizations, until electrical breakdown
UB = A + B log ρe (26) (EB) eventually occurs with visible sparks. They termed this
characteristic growth as mechanical breakdown (MB). For
where A and B are the constants depending on the electrolyte electrical breakdown (EB), they reported that current density
composition and the anodized metal.69,71,74,75 Figure 7 shows (j) has little effect on the breakdown potential (UEB), which is
the dependence of UB on log ρe during anodization of Nb, Ta, in line with the reports of Yahalom et al. and Ikonopisov et
Al, and Zr.69 It appears from the figure that the different al.69,76,82 In the case of mechanical breakdown (MB), however,
influences of ρe on UB defeat attempts to set the metals in series they observed that current density (j) has a significant effect on
with respect to the breakdown characteristics of their anodic the breakdown potential (UMB) according to the following
equation:
UMB = AMB + BMB log j (28)
where AMB and BMB are constants, which depend mainly on the
kind of anion in the electrolyte and slightly upon pH and
concentration of electrolyte: BMB > 0 for anodic oxides of
zirconium and titanium75,85 and BMB < 0 for anodic oxide of
tungsten.74
4.1.4. Other Factors Influencing Breakdown. The
surface state of the starting metal (i.e., the surface defects
(flaws), purity, processing history, etc.) also strongly influences
the breakdown potential (UB).61,86 In general, the surface
defects unavoidably cause a decrease of the breakdown
potential (UB) with the commencement of sparks.87 On the
other hand, post-breakdown anodization experiments have
shown that breakdown characteristics are independent of the
history of the anodic oxide film.72,88,89 When a valve-metal was
anodized in electrolyte A until breakdown occurred at UB,A, and
then the resulting sample was re-anodized in electrolyte B with
a higher breakdown potential (UB,B), the film formation during
the post-breakdown anodization continued at normal kinetics
until breakdown occurred at UB,B.88,89 Temperature (T) is one
Figure 7. Dependence of the breakdown potential (UB) on the of the easily controllable parameters of the electrolyte.
logarithm of electrolyte resistivity (ρe) for anodizations of Ta, Nb, Al, Ikonopisov formulated the temperature dependence of the
and Zr in solutions of ammonium salicyalte in dimethylformamide. breakdown potential UB (section 4.2.1).90 However, a change in
Reproduced with permission from ref 69. Copyright 1979 Elsevier. the electrolyte temperature can alter both the electrolyte
H dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
resistivity (ρe) and the property of the growing anodic oxide. je, x = 0 = α1 exp[α2E1/2] (31)
When the dependence of electrolyte resistivity (ρe) is
considered, no clearly pronounced dependence of the break- ln je, x = 0 = β1/T + β2
down potential (UB) on the temperature (T) was ob- (32)
tained.71,77,91
je, x = 0 = γ1ρe−γ2 (33)
4.2. Models for Breakdown
4.2.1. Electron Avalanche Multiplication. The first From eqs 30 and 31, the dependence of breakdown potential
attempt to develop a quantitative model of breakdown was (UB) on the electric field (E) is given by
made by Iknopisov.90 He considered experimentally observed
UB = (ψi /rq)(ln je,B − ln α1) − (ψiα2/rq) E (34)
breakdown characteristics, and noting that the breakdown
potential (UB) mainly depends on the nature of the anodized This equation explains a slight decrease of UB with increasing
metal and the electrolyte resistivity (ρe), he inferred that current density (j). Regarding the relation between the
breakdown is dependent upon the solid-state properties of the breakdown potential (UB) and temperature (T), the following
anodic oxide and is controlled by electrochemical reactions at expression is obtained by combining eqs 30 and 32:
the oxide/electrolyte interface. In his model, the initial
electrons are injected from the electrolyte into the oxide UB = (ψi /rq)(ln je,B − β1/T − β2) (35)
conduction band (CB) by either a Fowler−Nordheim or a
Schottky mechanism (Figure 8). The injected electrons Equation 35 predicts that UB is dependent on the temperature
(T), which conflicts with experimental observations.71,77,91 For
this discrepancy, Ikonopisov pointed out the interplay between
temperature (T) and the solution resistivity (ρe). For the
dependence of breakdown potential (UB) on the electrolyte
resistivity (ρe), from eqs 30 and 33, one may obtain
UB = (ψi /rq)(ln je,B − ln γ1 + γ2 ln ρe )
= (ψi /rq)(ln je,B − ln γ1) + (2.3ψiγ2/rq) log ρe (36)

Equation 36 has exactly the same form as eq 26, which
describes an empirical relation between UB and ρe.
Although Ikonopisov’s model explains some of the
experimental results, it has been criticized by many authors.
Shimizu pointed out the unrealistic value of the mean free path
λ(E) of ionized electrons, which from eqs 26, 29, and 36 is
given by
λ(E) = 1/α(E) = ψi /rqE = (1/2.3E)(B /γ2) (37)
By using the experimental values from Ikonopisov et al. for E
(=8.7 × 106 V cm−1) and B/γ2 (=1000 V), Shimizu obtained λ
Figure 8. Schematic representation of the band structure and the = 500 nm, which roughly corresponds to the thickness of oxide
avalanche breakdown in Ikonopisov’s model. Reproduced with films formed up to the potential 400 V and indicates the
permission from ref 79. Copyright 1984 The Electrochemical Society. absence of the electron avalanche capable of causing the
breakdown.94 Albella et al. questioned the origin of electrons in
Ikonopisov’s model.87 They pointed out Ikonopisov’s model
accelerate and multiply in avalanche during their travel in the
lacked a reasonable explanation of the role of the electrolyte
oxide of thickness (tox) to the anode, until the avalanche current
and the absence of specific electrochemical reactions required
reaches a critical value for breakdown. In this multiplication
for the injection of the initial electrons.
process, the electronic current (je) depends on the travel
Albella et al. explicitly considered the effect of the anodizing
distance (x) with x = 0 being the oxide/electrolyte interface,
electrolyte by posulating that the initial electrons for the
which can be expressed by
avalanche come from the electrolyte species incorporated into
je, x = t = je, x = 0 exp[α(E)tox ] = je, x = 0 exp[rqEtox /ψi] (29) anodic oxide.79−81 The incorporated electrolyte species act as
ox
impurity centers close to the oxide conduction band (CB),
where α(E) is the impact ionization coefficient at the electric releasing electrons to the conduction band via the field-assisted
field E, r is a recombination constant (r < 1), q is the electron Poole−Frenkel mechanism (Figure 9).80,87,95,96 In the model of
charge, and ψi is the threshold energy for impact ionization. Albella et al., the total current density (jt) consists of three
Breakdown occurs if the electronic current (je) exceeds a critical components:
value je,B at a critical oxide thickness (tox,B). Because UB = Etox,B,
jt = j1 + j2 + je (38)
the breakdown potential (UB) is given by
UB = (ψi /rq)(ln je,B − ln je, x = 0 ) where j1 is the oxidation current density, j2 is the current
(30)
density consumed by the incorporated electrolyte species and is
The dependences of je,x=0 on the electric field (E),69,92 assumed to be a constant faction γ of j1 (i.e., j2 = γj1), and je is
temperature (T), and electrolyte resistivity (ρe)93 were the electronic current density. The electronic current density
empirically determined to be, respectively: (je) at the anode can be expressed as
I dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
1 + φγ
V (t ) = Kj t
1+γ t (45)
γη E
ΔV (t ) = [exp(αU /E) − 1]
1+γα (46)
The factor (1 + φγ)/(1 + γ) in eq 45 describes the correction
of the anodizing rate due to the incorporation of electrolyte
species. On the other hand, eq 46 enforces deviation of
potential from the linearity due to the avalanche effect.
Accordingly, eq 44 predicts a gradual decrease of slope (dU/
dt) of the potential−time curve during galvanostatic anodiza-
tion. Albella et al. confirmed the validity of eq 44 by fitting it on
the experimental results of tantalum anodization (Figure 10).80
Figure 9. Band diagram showing the avalanche multiplication of

electrons in the model of Albella et al. The impurity level in
conduction band (CB) is denoted by “A”. Reproduced with
permission from ref 81. Copyright 1987 Elsevier.
je = je, x = 0 exp[αtox ]=je, x = 0 exp[αβU ] (39)

where α is the impact ionization coefficient, and β is the ratio of
the oxide thickness to the anodization potential (U) and is
equal to the inverse of the electric field E (i.e., β = 1/E = AR,
the anodizing ratio). Because the initial electronic current
originates from incorporated species, je,x=0 should be a constant
fraction η of oxyanion current (j2) and is je,x=0 = ηj2 = ηγj1.
Under the assumption that the critical current density is a
fraction z of the oxidation current j1, the breakdown potential
(UB) should satisfy the following relation:
je, x = 0 exp[αβUB] = zj1 (40)
Figure 10. Experimental result for the evolution of the potential (U)
Accordingly, the breakdown potential (UB) is given by as a function of time (t) during tantalum anodization in 1.2 M H3PO4
at 1.78 mA cm−2. The theoretical curve (solid line) has been fitted
UB = (1/αβ) ln(zj1 /j0 ) = (E /α) ln(z /ηγ) (41) according to eqs 44−46. Reproduced with permission from ref 80.
Copyright 1985 Elsevier.
The time derivative of the potential is given by
dU ⎛ 1 ⎞⎛ E ⎞⎛ M M2 ⎞ Further, by fitting eq 44 on the experimental potential

= ⎜⎜ ⎟⎟⎜ ⎟⎜⎜ 1 j1 + j⎟
x 2y2 2 ⎟⎠
evolutions in different electrolyte concentrations (C), they
dt ⎝ ρox ⎠⎝ F ⎠⎝ x1y1 (42) obtained a relation between γ and C:95
where ρox is the oxide density, F is the Faraday constant, and γ ≈ aC b (47)
M1 and M2 are the molecular weights of the oxide and the
incorporated species, respectively, whose corresponding anion with a and b being electrolyte-dependent constants. From eqs
and cation valences are x1,y1 and x2,y2, respectively. Combining 41 and 47, the concentration dependence of the breakdown
eqs 38 and 42 yields the following differential equation: potential (UB) is given by
UB ≈ (E /α)[ln(z /ηa) − b ln C ] (48)
dU /dt = Kjt (1 + φγ )[1 + γ + γη exp(αβU )]−1 (43)
which is in good agreement with the experiments.
where K is the unitary rate of anodization for oxide without 4.2.2. Stress-Driven Breakdown. Sato97 distinguished five
electrolyte incorporation and given by M1E/x1y1ρoxF, and φ is different possible contributions to the mechanical stresses in
the ratio of the equivalent weight of the incorporated species to anodic oxide: (a) electrostriction pressure, (b) interfacial
that of oxide, that is, φ = (M2/x2y2)/(M1/x1y1). Assuming a tension of the film, (c) internal stress caused by the volume
constant field in the oxide, the integration of eq 43 yields the expansion, (d) internal stress due to partial hydration/
relation between the anodizing potential (U) and time (t): dehydration of the anodic oxide, and (e) local stress caused
U (t ) = V (t ) − ΔV (t ) (44) by impurities. By considering the first two contributions as the
most general factors for breakdown, he mathematically derived
with V(t) and ΔV(t) given by a thermodynamic model of stress-driven breakdown, and
J dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
explained the breakdown potential (UB) and the effect of film pressure. The alignment of pores in a close-packed pattern
adsorbed anionic species on it. According to the model,97 the was considered to be a process of relieving the film stress. As
stress (ΔP) accumulated in the oxide film is equal to the breakdown in the anodic oxidation of aluminum proceeds,
therefore, a porous oxide layer progressively forms and thickens
ε(ε − 1) γ on the compact barrier oxide layer, of which thickness remains
ΔP = −
8π tox (49) constant with continuous plastic deformation. This electro-
striction-stimulated breakdown model is somewhat in line with
where ε is the oxide permittivity and γ is the surface tension. In the recent flow model accounting for the steady-state formation
eq 49, the first term represents the electrostriction effect and of porous AAO film by Skeldon et al. (see section 6.3.5).98
the second the interfacial tension effect. According to Sato, for
an oxide dielectric with ε > 10, an electric field (E) of 5 × 106 V 5. STRUCTURE OF POROUS ANODIC ALUMINUM
cm−1 produces a compressive electrostriction pressure exceed- OXIDE (AAO)
ing 1000 kg cm−2, which is higher than the critical mechanical
strength of oxides and thus may be a cause of their mechanical 5.1. General Structure
failure. Because the compressive stress within the anodic oxide Figure 12 shows schematically an idealized structure of porous
increases with thickness, there is a limiting oxide thickness AAO, together with scanning electron microscopy (SEM)
(tox,B) above which breakdown occurs. The incorporated images of each part of the porous AAO. Porous AAO has a
anionic species causes a decrease in the surface tension (γ), honeycomb-like structure. Porous oxide layer formed on
and thus increases the stress by lowering the value of the aluminum substrate contains a large number of mutually
second term in eq 49. The dependence of the breakdown parallel pores. Each cylindrical nanopore and its surrounding
potential (UB) on the anion concentration (CA−) in the oxide constitute a hexagonal cell aligned normal to the metal
electrolyte was also established, as follows: surface. Each nanopore at the metal/oxide interface is closed by
dUB 8πkT a thin barrier oxide layer with an approximately hemispherical
=− ΓA− morphology. Under proper anodization conditions, the oxide
d ln C A− ε(ε + 1) (50) cells are self-organized to form a hexagonally close-packed
where ΓA− is the anion density at the oxide surface at the structure.7 On the other hand, the surface of the aluminum
breakdown potential (UB). The model predicts a lower after complete removal of the porous oxide layer is textured
breakdown potential for electrolytes having higher anion with arrays of concave features. The thickness of the porous
concentration. Kato et al. have also used electrostriction to AAO layer on aluminum is proportional to the total charge
explain the enhancement of breakdown by incorporated anionic (Qc) involved in the electrochemical oxidation. Therefore, the
impurities (see eq 27).77 They suggested that the incorporated depth of oxide nanopores is easily tunable from a few tens of
anions lead to additional electrostrictive input into the nanometers up to hundreds of micrometers by controlling
mechanical stress in oxide films. anodization time (t). In general, the structure of self-ordered
Sato noted three different forms of mechanical breakdown porous AAO is often defined by several structural parameters,
depending on the mechanical property of the films: brittle crack such as interpore distance (Dint), pore diameter (Dp), barrier
for rigid anhydrous anodic oxides, and plastic deformation or layer thickness (tb), pore wall thickness (tw), pore density (ρp),
flow for visco-plastic hydrous anodic oxides (Figure 11).97 He and porosity (P). For ideally ordered porous AAO, the
suggested that the formation of porous AAO films on following relationships can be drawn by simple geometric
aluminum is associated with continuous mechanical breakdown, consideration:
accompanied by a continuous plastic flow of oxide under high Dint = Dp + 2tw (in nm) (51)
⎛ 2 ⎞
ρP = ⎜ 2
⎟ × 1014 cm−2
⎝ 3 Dint ⎠ (52)
⎛ π ⎞⎛ Dp ⎞
P(%) = ⎜ ⎟⎜ ⎟ × 100
⎝ 2 3 ⎠⎝ Dint ⎠ (53)
These structural parameters of porous AAO are known to be
dependent on the anodizing conditions: the type of electrolyte,
anodizing potential (U), current density (j), temperature (T),
etc. Among those, anodizing potential (U) and current density
(j) are the most important electrochemical parameters. A
review on this matter has recently been published by Sulka.99
Here, we briefly discuss the major structural parameters of
porous AAO and the electrochemical factors influencing them.
5.1.1. Pore Diameter (Dp). O’Sullivan and Wood used
electron microscopy to quantitatively study the morphology of
porous AAO potentiostatically formed in phosphoric acid
(H3PO4) electrolyte.100 The pore diameter (Dp), interpore
distance (Dint), and barrier layer thickness (tb) were observed to
Figure 11. Three modes of mechanical breakdown of surface films. be directly proportional to the anodizing potential (U). Their
Reproduced with permission from ref 97. Copyright 1971 Elsevier. microscopic analysis revealed that the pore diameter increases
K dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
Figure 12. Schematic structure of (a) porous anodic aluminum oxide (AAO) on Al foil and (b) cross-sectional view. (c−e) SEM images of porous
AAO, showing top surface, barrier layer, and bottom surface, respectively. Scale bars are 1 μm. Panels c−e were reprinted with permission from ref
111. Copyright 2006 Macmillan Publishers Ltd.: Nature Materials.
at the rate (ζp) of 1.29 nm V−1 with respect to the anodizing

potential (U):
DP = ζp·U = 1.29·U (54)
They pointed out that the electrolyte concentration does not

significantly influence the pore diameter (Dp), while the
temperature of the electrolyte is positively correlated with
pore diameter.100 On the other hand, theoretical modeling of
porous AAO growth performed by Parkutik and Shershulsky
predicted a decrease in pore diameter with decreasing
electrolyte pH (i.e., increasing electrolyte concentration) due
to the enhanced dissolution velocity of anodic oxide at the pore
base.101 Moreover, a recent study by Sulka and Parkoła
indicated that the pore diameter decreases with decreasing
temperature.102 In general, pore diameter close to the surface of
a porous AAO film is larger than that close to the pore bottoms
(i.e., truncated pore channels), especially when anodization is Figure 13. Cross-section SEM micrographs of AAOs prepared from
conducted at an elevated temperature and/or for an extended two separate anodization experiments, whose reactions were
period of time. This can be attributed to the chemical terminated near j = 86 mA cm−2 and j = 881 mA cm−2 in sinusoidally
dissolution of the pore wall oxide by acid electrolyte. oscillating currents under potentiostatic condition (U = 200 V). (c) A
Accordingly, pore diameter measured from the pore bottom schematic cross-section of AAO on Al. (d) The parameters defining
(not from the surface of AAO film) is more relevant for the geometry of the pore bottom. Scale bars = 250 nm. Reproduced
with permission from ref 103. Copyright 2010 Wiley-VCH Verlag
investigating the intrinsic effect of electrochemical parameters GmbH & Co. KGaA, Weinheim.
on the structure of porous AAO.
Recently, Lee et al.103 reported that pore diameter (Dp)
increases with current density (j) under potentiostatic during potentiostatic hard anodization (HA) at the potential
anodization conditions (Figure 13). Under specific experimen- range of 140−200 V (see section 7.2). They suggested that at a
tal conditions, they observed spontaneously oscillating current given potentiostatic condition (i.e., U = constant) the
L dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
distribution of the current lines and electric field (E) may be V−1.7,100,114 For self-ordered porous AAOs formed by mild
sensitively varied by the geometric details of the barrier oxide anodization (MA, see section 7.1) in oxalic and phosphoric acid
layer. That would influence the movement rates of the at various anodizing potentials (U), Vrublevsky et al. have
electrolyte/oxide and oxide/metal interfaces, hence the pore reported empirical equations based on results from their re-
diameter (Dp).103 anodizing experiments.115−117 They used the equations for
5.1.2. Interpore Distance (Dint). It has long been estimating the barrier layer thickness by assuming the anodizing
established that the interpore distance (Dint) is also linearly ratio, ARMA = 1.14 nm V−1. On the other hand, reduced
proportional to the anodizing potential (U).7,100,104−109 A anodizing ratios for sulfuric and oxalic acid have recently been
detailed study on this matter was performed for sulfuric and reported for hard anodization (HA); ARHA = 0.6−1.0 nm V−1
oxalic acid by Ebihara et al.104,105 Their empirical expressions (see Figure 13d and section 7.2).18,111,113,118,119 Chu et al.18
on the relationship between the interpore distance (Dint) and determined the anodizing ratio for less-popular anodizing
anodizing potential (U) are as follows: electrolytes (e.g., tartaric, citric, glycolic, and malic acids) by
performing what they termed “critical-potential anodization”.
for sulfuric acid: Dint = 12.1 + 1.99 ·U (U = 3−18 V)
The anodizing ratio for various electrolytes was determined to
(55) be AR ≈ 1 nm V−1 (Figure 14). It should be noted that this
for oxalic acid: Dint = 14.5 + 2.00 ·U (U ≤ 20 V) value of anodizing ratio is the averaged proportionality constant
(56) determined from mild and hard anodization experiments of
aluminum.
=−1.70 + 2.81·U (U ≥ 20 V) (57)
For oxalic acid-based anodizations in the potential range of 20−
60 V, Hwang et al. reported that interpore distance only
depends on anodizing potential (U), not on the temperature of
the electrolyte:107
for oxalic acid: Dint = −5.2 + 2.75 ·U (U = 20−60 V)
(58)
This temperature independence of the interpore distance is in
line with the results of Keller et al.,7 but conflicts with the
experimental results of Sulka and Parkoła,102 who observed that
interpore distance is positively correlated with temperature for
self-ordered porous AAOs formed by sulfuric acid-based
anodization; interpore distance at an elevated temperature
(10 °C) is about 10% larger than that at a low temperature (i.e.,
−8 to 1 °C). O’Sullivan and Wood100 reported for phosphoric
acid-based anodization that increasing the temperature or the
electrolyte concentration decreases the interpore distance. For
self-ordered porous AAOs formed by mild anodization (MA) Figure 14. Effect of anodizing potential (U) on the barrier layer
conditions using sulfuric, oxalic, and phosphoric acid, it has thickness (tb) for porous AAO formed in different acid electrolytes.
generally been accepted that the interpore distance (Dint) is (Solid symbols, measured values; open symbols, calculated values from
linearly proportional to the anodizing potential (U) with a the half-thickness of the pore walls). Reproduced with permission
proportionality constant ζMA of 2.5 nm V−1 (see section from ref 18. Copyright 2006 The Electrochemical Society.
7.1):109
Dint = ζMA ·U = 2.5·U (59) 5.2. Structure of Pore Wall (Anion Incorporation)
However, this empirical formula is not valid for hard The incorporation of electrolyte-derived anions into anodic
anodization (HA), under conditions in which a high electric alumina is considered a general phenomenon for both barrier-
field (E) is exerted across the barrier layer due to high current and porous-type anodization, occurring least for the former and
density (j) during anodization.16,110−113 This will be discussed greatest for the latter.3 For three major pore-forming acid
in detail in section 7.2. electrolytes (e.g., H2SO4, H2C2O4, and H3PO4), incorporation
5.1.3. Barrier Layer Thickness (tb). The thickness of the of acid anions occurs via inward migrations under an electric
barrier layer (tb) is one of the most important structural field (E) during the anodization of aluminum. The incorpo-
parameters of porous AAO for understanding the kinetics of rated acid anions influence the chemical, optical, and
the electrochemical oxidation of aluminum. Like other mechanical properties of the resulting porous AAO. For
structural parameters, barrier layer thickness (tb) is also example, incorporated oxalate (C2O42−) anions together with
dependent on the anodizing potential (U). The potential singly ionized oxygen vacancies (F+ center) have been known
dependence of the barrier layer thickness has also been known to contribute to the blue photoluminescence (PL) of porous
as “anodizing ratio (AR = tb/U)”, the inverse of which AAO formed in oxalic acid solution.120−122 The mechanical
corresponds to the electric field (E) across the barrier layer, and properties (e.g., hardness, wear resistance, and elasticity) of
it determines the ionic current density (j) (see eq 1). anodic alumina are also known to be affected by the
Accordingly, at a given anodizing potential (U), current density incorporated chemical species (e.g., water and acid
(j) increases exponentially as a function of the inverse of the anions).123−125 The amount of incorporated acid anions and
anodizing ratio AR (i.e., the electric field strength E). Earlier their distribution in anodic alumina depend on the anodization
studies have indicated that the anodizing ratio equals 1.2 nm potential (U), current density (j), and temperature (T), as well
M dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
Figure 15. (a) Schematics illustrating the duplex structure of pore walls of porous AAO: vertical (left) and transverse (right) cross-sections. TEM
plane view (b) of H3PO4-AAO and the corresponding X-ray maps of the elements: (c) phosphorus, (d) oxygen, and (e) aluminum. (f) TEM plane
view of H3PO4-AAO, showing the different parts of the pore wall (i.e., the outer pore wall, cell-boundary band, and interstitial rod). Reproduced with
permission from ref 135. Copyright 2009 Elsevier.
as the type and concentration of electrolytes.44,117,126−129 bands are composed of relatively pure alumina, whereas the
Accordingly, the chemical structure of the pore wall of AAOs material adjacent to the pores contains incorporated phosphate
varies with the anodization conditions. Han et al.129 have species from the electrolyte.133,134 Recent microscopic chemical
recently reported that, even at a steady-state growth condition analyses of the pore wall material of highly ordered H3PO4-
(i.e., fixed U, j, and T), the content of anionic impurities and AAO by Le Coz et al.135 clearly indicated the presence of
their incorporation depth decrease as a function of anodization phosphorus-free cell-boundary bands (Figure 15b−e). The
time due to the progressive reduction of the electrolyte different parts of the unit cell were found to have a
concentration, which markedly affects pore widening as well as heterogeneous chemical composition of Al2O3·0.197AlPO4·
the opening of the barrier oxide layer by wet-chemical etching.
0.034H2O, which supports the results of the previous works by
On the basis of TEM investigations of disordered porous
AAOs formed in sulfuric, oxalic, phosphoric acid solutions, Thompson et al.10,130 The work also highlighted, as a new
Thompson and co-workers suggested that pore wall oxide has a finding, that there is an interstitial rod material with a
duplex structure in terms of chemical composition: an acid- composition of Al2O3·0.018AlPO4·xH2O at the triple junction
anion contaminated outer oxide layer next to the pores and a connecting three cells (Figure 15f).135
relatively pure inner oxide layer, as schematically shown in Thompson and Wood related the steady-state anodizing
Figure 15a.130 TEM micrographs of porous AAO films formed behavior of porous AAO films formed in the major anodizing
in phosphoric and oxalic acids (i.e., H3PO4-AAO and H2C2O4- acids to the distribution of the acid anions within the barrier
AAO) showed a cell structure with cell-boundary bands, layers and the true field strengths across the relatively pure
although the cell-boundary band in H2C2O4-AAO did not alumina regions.14 Starting with the knowledge that the
appear as well-defined as that observed in H3PO4-AAO. The thickness ratio of the inner to outer pore wall oxide layer
cell-boundary bands became markedly more apparent upon increases in the order sulfuric acid < oxalic acid < phosphoric
continued exposure to the electron beam due to the preferential acid < chromic acid, they depicted the same order of thickness
crystallization of the cell boundary regions. Meanwhile, the ratio for the barrier oxide at the bottom of pores and correlated
presence of a cell-boundary band was not apparent for porous it to the rates of oxide formation at the same anodizing
AAO films formed in sulfuric acid (i.e., H2SO4-AAO). The potential (U). The averaged effective electric field (E = ΔU/tb)
duplex structure of the pore walls was confirmed by Ono and across the barrier layer is approximately constant for the barrier
Masuko,131 who reported that the depth and the amount of
layers of AAOs formed in different acid electrolytes, because
anion incorporation in H3PO4-AAO increased linearly with
anodizing potential (U), but the presence of a duplex structure the measured anodizing ratios are similar (ARMA = tb/ΔU ≈ 1.2
was not confirmed by TEM for samples formed at U < 10 V. nm V−1). On the other hand, the potential drop (ΔU) is
They also found that the crystallization rate of pore wall oxide greater and linear across the relatively pure alumina region and
under a strong electron-beam irradiation decreases with the smaller across the outer acid anion-contaminated region, where
increasing content of incorporated electrolyte species.132 the potential decreases progressively toward the oxide/
Scanning transmission electron microscopy (STEM) and electrolyte interface (Figure 16). Therefore, the true electric
energy dispersive X-ray (EDX) point analysis on H3PO4-AAO field across the relatively pure alumina region of the barrier
by Thornton and Furneaux revealed that the cell-boundary layer is in the order:
N dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
H 2SO4 −AAO > H 2C2O4 −AAO > H3PO4 −AAO

> H 2CrO4 −AAO
Figure 16. Distribution of the potential drop and electric field, E

(slope of the voltage−distance plot), across barrier layers of porous
AAOs formed in (a) sulfuric, (b) oxalic, (c) phosphoric, and (d) Figure 17. (a) The evolution of pore diameter (Dp) as a function of
chromic acid. Reproduced with permission from ref 14. Copyright time (tetch) upon wet-chemical etching of porous AAOs formed in 0.3
1981 Macmillan Publishers Ltd.: Nature. M oxalic acid at 40 V. Wet-chemical etchings of pore wall oxide were
performed in 5 wt % H3PO4 at 29 °C. The numbers in the plot are the
slopes (in nm min−1) of the corresponding linear fits. (b) SEM images
showing systematic increase in pore diameter (Dp) as a function of
Accordingly, the rate of formation of the anodic oxide films time (tetch) upon wet-chemical etching in 5 wt % H3PO4 (29 °C).
in the different acids varies with the same order given above if Reproduced with permission from ref 129. Copyright 2013 The
solid-state ionic migration across the inner layer is the rate- American Chemical Society.
determining step.14 The current density (j) is related to the
potential drop (ΔU) across the barrier oxide by the high-field
conduction theory (eq 1). Among the acid electrolytes above, ability to precisely control the pore diameter by the pore
sulfuric acid will give the highest current density (j), because of widening process is one of the most attractive features of
the highest potential drop across the relatively pure alumina porous AAO for template-based nanofabrication. This feature
region adjacent to the metal interface. allows one to systematically investigate the size dependence of
The duplex nature of the pore wall can be experimentally chemical or physical properties of ordered arrays of nanodots,
evidenced by investigating the rate of pore widening. For a nanowires, or nanotube materials prepared from porous AAO
given set of etching conditions (i.e., temperature and templates.
concentration of an etchant solution, typically H3PO4), the As-prepared porous AAOs are amorphous and contain
rate of etching is dependent on the chemical composition of the varying amounts of water depending on anodizing condition.3
pore wall oxide of AAO.129 Figure 17 shows (a) the evolution The local coordination environments of aluminum in
of pore diameter (Dp) as a function of pore wall etching time amorphous AAOs have been extensively studied using X-ray
(tetch) for porous AAO formed in 0.3 M oxalic acid (H2C2O4), radial distribution analysis,136 electron-yield extended X-ray
together with (b) representative SEM micrographs. As absorption fine structure (EXAFS) spectroscopy,137 and magic-
presented in Figure 17a, Dp versus tetch plot is characterized angle spinning nuclear magnetic resonance (27Al MAS
by an inflection point, at which the slope of the curve changes. NMR).138−141 Amorphous AAOs have been considered to
Pore wall oxide in the early stage is etched at a higher rate (1.04 have a close structural relation to spinel (fcc) γ-Al2O3 with
nm min−1) than that (0.36 nm min−1) in the later stage. The tetra- and hexa-coordinated aluminum cations in the mixing
retarded rate of etching in the later stage can be attributed to ratio of 1:2. Farnan et al.138 have reported that the coordination
the relatively pure nature of the inner pore wall oxide, as numbers of aluminum cations are dependent on the anodizing
compared to the less dense outer pore wall oxide due to the electrolyte: hexa-coordination for porous AAO formed in
incorporation of anionic species. As shown in Figure 17b, the chromic acid (i.e., H2CrO4-AAOs), tetra-, penta-, and hexa-
O dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
coordination for H2SO4- and H2C2O4-AAOs, and tetra- and thermodynamically stable hcp α-Al2O3 (corundum) is obtained
penta-coordination for H3PO4-AAOs. It is now generally above 1150 °C. Crystalline phase transformations of porous
accepted that the aluminum exists in four-, five-, and six-fold AAOs formed in different electrolytes have also been
coordination with oxygen, although the ratio of the investigated by thermogravimetric (TG) and differential
coordination numbers varies in different samples formed in scanning calorimetry (DSC) analyses.139,140,144,147−151 The
different anodizing conditions. Farnan et al.138 attributed such results have indicated that the type of anodizing electrolytes
variations of aluminum coordination to the presence of (i.e., the nature of incorporated acid anions) strongly influences
hydroxyl groups (−OH) within alumina, with an increase of transformation temperatures during heat treatment. For
anodizing temperature favoring the hexa-coordination. Incorpo- H2C2O4-AAOs, Mardilovich et al.144 reported that dehydration
rated electrolyte species (e.g., acid anions, proton, and water) occurs up to 400 °C, dehydroxylation occurs at 400−700 °C,
may be more responsible for such variations of aluminum and incorporated oxalates pyrolyze at higher temperatures
coordination. Yet, a clear explanation for such variation of before the final transformation into thermodynamically stable
coordination number has not been given yet. α-Al2O3. A comparative study of H2SO4-, H2C2O4-, and
H3PO4-AAOs by Mata-Zamora et al.150 has shown that
5.3. Effect of Heat Treatments
incorporated phosphates are stable up to 1400 °C, while
The surfaces of pore walls are hydrophilic due to the surface- sulfates and oxalates decompose into gaseous SO2 and CO2 at
bound hydroxyl (−OH) groups, and this feature allows easy 900 and 870 °C, respectively. Later, Kirchner et al.140
modifications of the surface property via self-assembly of confirmed decomposition of sulfates in H2SO4-AAOs at around
various functional molecules. Extensive recent reviews on this 900 °C by mass spectrometry (MS).
matter are given in refs 142 and 143. On the other hand, as- In general, the initial crystallization and subsequent phase
prepared porous AAOs are highly labile to both acid and base transformation of porous AAO are accompanied by changes in
attack. Proper high temperature heat treatments of as-prepared the morphology of pores and also in mechanical proper-
porous AAOs markedly improve their thermal stability and ties.139,144,151 MacQuaig et al. reported ∼6.7% loss of pore
resistance against acid, base, and other corrosive chemicals, circularity, ∼15% increase in pore diameter (Dp), ∼13%
allowing the resulting AAOs to be useful as starting materials decrease in pore density (ρ), and about a 2-fold increase in
for developing various devices, which will operate in high microhardness (from 2.5 to 4.7 GPa) upon heat-treatment of
temperatures or harsh environments. TEM and X-ray as-prepared H2C2O4-AAO up to 1200 °C.151 They attributed
diffraction (XRD) studies have indicated that the porous the changes of the overall pore structure to the densification of
AAOs undergo a series of polymorph transformations upon pore wall materials, which is associated with dehydration,
heat treatment up to 1500 °C in air with the following route dehydroxylation, and the loss of incorporated acid anions in the
(see Figure 18 for XRD): amorphous AAO → γ-Al2O3 → δ- course of the phase transformations from amorphous to
Al2O3 → θ-Al2O3 → α-Al2O3.121,139,140,144−147 Amorphous crystalline α-Al2O3. Mardilovich et al. observed sharp decreases
AAOs crystallize into almost pure γ-Al2O3 at a temperature in the flexibility of H2C2O4-AAO films at the onset of
range of 820−900 °C, and then undergo successive trans- crystallization at 820−840 °C and on phase transformation
formations through metastable ccp δ- and θ-Al2O3 until from metastable ccp-alumina to hcp-alumina (i.e., α-Al2O3) at
1100−1150 °C.144 They pointed out that the fragility of porous
α-Al2O3 membranes is so high that they cannot be considered
for routine practical use as membranes. High temperature
treatment of initially planar porous AAO membranes often
leads to serious mechanical deformation (e.g., curling/rolling)
or even cracking.139,144,148 Therefore, careful heat-cycling
processing is required. Recently, Chang and co-workers
reported that severe deformation of porous AAO membranes
can be prevented by removing the acid-anion contaminated
outer pore wall oxide before annealing at high temperatures.152
A proper hydrothermal treatment of H3PO4-AAOs improved
crystallinity of the relatively pure inner oxide layer (i.e., the cell-
boundary band in Figure 15), which enhanced the etching
contrast between the inner and outer oxide layers, after which
the outer pore wall oxide was selectively removed from the unit
cells of the AAO membranes by wet-chemical etching.
Deformation-free porous α-Al2O3 membranes could be
obtained by annealing of the resulting samples at 1300 °C
(see Figure 19).
6. GROWTH OF POROUS ANODIC ALUMINUM OXIDE

(AAO)
6.1. Stress Generation in Anodic Oxide Films
6.1.1. Volume Expansion. Oxidation of aluminum is a
Figure 18. XRD spectra of heated H3PO4-AAO (Co Kα radiation). volume expansion process. The volume expansion during
Key: AlP = AlPO4, A = α-Al2O3, T = θ-Al2O3. Reproduced with anodization can be quantitatively expressed by the Pilling−
permission from ref 139. Copyright 2005 Elsevier. Bedworth ratio (PBR). The PBR is rigorously defined by the
P dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
Figure 20. A schematic illustration of volume expansion during

anodization of aluminum.
For three major pore-forming acid electrolytes (i.e., H2SO4,

H2C2O4, and H3PO4), a wide range of volume expansion
factors (kv) between 0.86 and 1.90 have been reported (Table
1).106,116,162,163,165−168 For anodizations of aluminum in
H2SO4, Jessensky et al.165 investigated the relation between
the volume expansion factor (kv) and the degree of self-
ordering of pores. They reported that optimal conditions for
the best ordered arrays of pores are accompanied by a moderate
volume expansion (i.e., kv = 1.22), while contraction or very
strong volume expansion can result in the disordering of pores.
Figure 19. A photograph of the porous α-Al2O3 membranes obtained Further, they proposed that the mechanical stress at the metal/
by annealing the porous AAOs with (a) and without (b) acid-anion oxide interface, which is associated with volume expansion and
contaminated outer pore walls. (c−e) SEM images of porous Al2O3 increases with the anodizing potential (U), is the driving force
membranes obtained by annealing the porous AAOs after removal of for the formation of ordered hexagonal pore arrays, by causing
outer pore walls at (c) 1115 °C, (d) 1250 °C, and (e) 1300 °C; the repulsive forces between the neighboring pores. Li et al.
scale bars are 1 μm. Reproduced with permission from ref 152. reported a similar line of experimental results, noting that the
Copyright 2012 The Royal Society of Chemistry. volume expansion factor (kv) for the optimum anodization
conditions required for ordered pore arrays should be close to
molar volume ratio of grown oxide (Vox) to the consumed 1.4, irrespective of the anodizing electrolytes (i.e., H2SO4,
metal (Vm) as follows: H2C2O4, or H3PO4).106 Later, on the other hand, Nielsch et al.
proposed that the best self-ordering of pores requires a porosity
Vox Mox ρm (P) of 10%, the condition that corresponds to a volume
PBR = =
Vm nM mρox (60) expansion of porous AAO of about 1.23, independent of the
electrolyte.109
where Mox is the molecular weight of oxide, Mm is the atomic More systematic investigations on the effect of anodization
weight of metal, n is the number of atoms of metal per one conditions on the volume expansion factor (kv) have been
formula of the oxide, and ρm and ρox are the densities of metal performed by Vrublevsky and co-workers. For porous AAO
and oxide, respectively. In science on the corrosion of metals, growths in H2SO4 and H2C2O4 electrolytes, they determined
PBR has been the basis for judging the protectiveness of a that the volume expansion factor (kv) has a linear dependence
passivating oxide: if PBR < 1, the passivating oxide is under on the anodizing potential (U) and also noted a linear relation
tensile stress and easily cracked; if 1 < PBR < 2, the oxide between the logarithm of the current density (i.e., ln j) and the
covers the metal uniformly and is protective; if PBR > 2, the inverse volume expansion factor (i.e., 1/kv).116,163,167 For
passivating oxide is under too much compressive stress and anodizations under galvanostatic conditions, an increase of
easily crumbles (e.g., iron oxide on iron).153,154 For anodic temperature led to a decrease of the volume expansion factor
alumina growth, PBR can be experimentally determined from (kv) due to the corresponding decrease of the formation
the current efficiency (ηj) of oxide formation and the density potential (U), in which the slopes of ln j versus 1/kv curves are
(ρAAO) of the resulting AAO, provided that the composition of invariant with respect to the anodizing temperature.163,167
anodic oxide is well-defined. The densities of barrier- and However, the slopes of curves were found to be different for
porous-type AAOs have been reported to be in the range of different electrolytes, which was explained by the influence of
ρAAO = 2.7−3.5 g cm−3.104,111,155−157 Assuming composition acid-anion incorporation on the volume expansion: the larger is
stoichiometry of Al2O3 and ρAAO = 3.0 g cm−3, PBR for AAO the amount of incorporated acid anions, the larger is the
growth is 1.70 at 100% current efficiency (ηj). For porous-type volume expansion factor (kv).167 On the basis of the
AAO growth, on the other hand, PBR can vary between 1.02 experimental results of Vrublevsky et al., one may obtain the
and 1.58 due to the lower current efficiency (ηj = 60− following relation:
93%).158−161 The exact determination of PBR is rather
complicated by the composition of anodic oxide, its density,
and the current efficiency (ηj) of oxide formation. Con-
sequently, volume expansion in anodic oxide growth has been
considered instead, by employing a volume expansion factor 6.1.2. Stress Measurements. Anodic alumina is a
(kv), and a simple thicknesses ratio:116,162−164 dielectric material. During anodization, a very large electric
k v = hAAO/hAl field (typically, 106−107 V cm−1) is impressed on the oxide
(61)
film. The electric field drives the inward movement of O2− ions
where hAAO and hAl are the vertical heights of the AAO and the and the outward migration of Al3+ ions within the anodic oxide.
consumed aluminum, respectively (Figure 20). The resistance to these counter-migrations and the attraction of
Q dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
Table 1. Volume Expansion Factors (kv) Reported for Porous Anodic Aluminum Oxide (AAO) Growth in Three Major Pore-
Forming Acid Electrolytes
electrolyte concentration temp (°C) Ua or jb kvc refs
H2SO4 20 wt % 1 18−25 V 0.86−1.62 165
20 wt % 1 19 V 1.41 106
1.7 wt % 1 25 V 1.36 106
1.7 wt % 10 25 V 1.40 106
10 wt % mixture solutiond 6−20 mA cm−2 1.4−1.6 167
18−22 50 V 1.72 162
0 100 V 1.76 162
300 V 1.90 162
H2C2O4 2.7 wt % 1 40 V 1.42 106
0.34 M 15 40 V 1.18 168
0.22−0.92 M 16−18 1.62−4.8 mA cm−2 1.25−1.42 163,167
H3PO4 0.1−2.9 M 18 2−13 mA cm−2 1.2−1.62 166
a
U = anodizing potential (in V). bj = current density (in mA cm−2). ckv = volume expansion factor. dA mixture solution of 0.41 M H2SO4 and 0.16
M H3BO3.
the charged species result in a compressive electrostatic stress and Leach50 conducted deflection measurements on aluminum
along the direction of the electric field. The compressive stress and reported the effects of current density and oxide thickness
normal to the oxide surface is proportional to the dielectric on the stress. During anodization of aluminum in ammonium
constant (ε) and the square of the electric field (E):169 borate and ammonium citrate solutions, they observed that the
ε 2 stress can be either tensile or compressive depending on the
σ⊥ = E current density. Compressive stress was observed below 1 mA
8π (62)
cm−2, while tensile stress was observed at higher current
This compressive stress occurs only under the electric field. densities. A similar line of results was obtained by Nelson and
Thus, the stress will relax when the anodization is stopped. Oriani,169 who performed deflection measurements during
Proost et al. have determined electrostatic stress in anodic oxide anodization of aluminum and titanium in 0.1 M H2SO4. The
films of thickness tb as follows:67,170 deflection was related to the stress as follows:169
v ε − (α1 + α2) E2 EMt 2Δk
σ ES = − ε0 σ =
1−v 2 tb (63) 2
3(1 − vM )L2tb (65)
where v is the Poisson coefficient of the oxide film, ε is its
relative dielectric constant, εo is the vacuum permittivity, and α1 where EM and vM are the elastic modulus and Poisson’s ratio of
and α2 are both characteristic electrostriction constants. metal strip of length, L, and thickness, t; tb is the thickness of
Porous AAO has been known to incorporate water as well as the oxide layer where the stress is generated; Δk is the radius of
varying amounts of electrolyte-derived anionic species (see curvature of the metal strip. The compressive stress due to
section 5.2). Compositional effects arising from anion electrostriction was found to increase linearly with anodizing
incorporation and oxide inhomogeneities may be sources of potential during oxide growth. Slowly grown oxides have
stress in anodic oxides. The stress during anodization can be greater electrostrictive deflections than more rapidly grown
measured by monitoring the changes of the substrate oxides. For aluminum anodized in 0.1 M sulfuric acid, the
deflection. Stoney related the measured deflection (i.e., the deflections are compressive at low current densities and
radius of curvature) to the stress (σ) as follows:171 become tensile above 0.6 mA cm−2. The development of
tensile stress was attributed to the volume difference between
Yt 2 the metal being oxidized and the oxide formed at the metal/
σ= oxide interface.169 Moon and Pyun investigated the effect of
6Δktb (64)
electrolyte concentration and current density on the deflection
where Y is Young’s modulus of the substrate metal, t is the behavior of aluminum in sulfuric acid.173,174 Their experiments
thickness of the metal foil, tb is the thickness of the oxide on the found that the deflections become more tensile as the current
metal, and Δk is the radius of curvature. Equation 64 has been density increases. Compressive stresses were always observed at
modified over the decades to account for lateral strain, the relatively low current density (j = 2 mA cm−2). On the
differences in the elastic moduli of the oxide and its metal other hand, at larger concentrations of sulfuric acid, the rates of
substrate, and non-uniformity of the stress distribution in the deflection with respect to the current density became nonlinear.
oxide. Vermilya172 applied the Stoney method for anodizing The observed compressive stress at low current densities and
different metals. Upon applying potential, the substrate tensile stress at higher current densities was explained in terms
deflected, indicating tensile stress. The stress observed with of the annihilation of cation vacancies and the formation of
the forming voltage applied was always more compressive than oxygen vacancies at the metal/oxide interface, respectively. The
at zero voltage except for tungsten. Higher stress was observed authors suggested that the stresses that developed are not
when the rate of oxide formation was high. Vermilya attributed distributed over the entire oxide film, but are limited to a
the observed stress to a dynamic hydration process. As the narrow region of the metal/oxide interface below 1 nm.174 An
oxide film is buried by newly generated oxide, it is dehydrated opposite evolution of internal stress has recently been reported.
by proton migration, producing tension in the film. Bradhurst Proost et al.175 measured the internal stress of porous AAO
R dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
during the very initial stage of pore formation in 0.4 M

phosphoric acid by employing a high-resolution in situ
curvature measurement technique based on multiple-beam
deflectometry. The internal stress was found to remain constant
during the initial barrier growth. However, the internal stress
value increases in the compressive direction with increasing
current density. When the current density is lower than 4 mA
cm−2, the internal stress in the barrier oxide is tensile, while at
higher current densities, the internal stress becomes compres-
sive. The different stress evolutions in different electrolyte
systems have not yet been fully understood. More systematic in
situ measurements of stress as a function of the anodizing
conditions at the very initial stage of pore formation are
required to resolve conflicting stress evolutions reported in the
literature. A meaningful advance in this direction has recently Figure 21. Cross-sectional SEM images of the AAO confined in a
been made by Hebert and co-workers,176 who demonstrated micrometer-sized vertical trench pattern: (a) low and (b) high
the effectiveness of phase-shifting curvature interferometry as a magnification image. Scale bar = 1 μm. Reproduced with permission
new technique for high-resolution in situ monitoring of stress from ref 181. Copyright 2006 The Electrochemical Society.
evolution during anodization. The newly developed metrology
allows extremely stable and reliable measurement of curvature
changes at a curvature resolution of 10−3 km−1, which is Retardation of anodization rate has also been reported for
comparable to or higher than that of the high-resolution lateral anodization processes. In that process, an aluminum thin
film deposited on a substrate is sandwiched by a rigid insulating
multiple-beam deflectometry technique.175,177−179 From stress
top layer, and then the side edges of the aluminum are anodized
measurements during galvanostatic anodizing of aluminum in
to produce horizontal arrays of pores on the substrate.182−186
0.4 M phosphoric acid, Hebert and co-workers176 found that
Oh and Thompson186 reported abnormal behavior in the
the apparent stress in the barrier oxide is tensile (+100 MPa) at
anodic oxidation of aluminum in mechanically confined
low current density but became increasingly compressive at
structures used for the formation of horizontal nanoporous
higher current densities. In addition, they observed that
AAO. The authors observed that dendrites, periodic internal
transition from tensile to compressive stress occurs at current
pore structures (see Figure 22a), formed with a 5% retarded
density of 4 mA cm−2, in good agreement with the report of
growth rate, as compared to its value during bulk anodization
Proost and co-workers.175
under the same conditions. They attributed the observed
6.1.3. Effects of External Stresses on Pore Growth. The
anomalies to the suppressed volume expansion and a plastic
effect of an applied external tensile stress on the self-ordering of
flow of anodic oxide confined by an insulating top layer;
pores was first studied by Sulka and co-workers.180 It was found
because volume expansion by plastic flow in the pore growth
that the magnitude of applied tensile stress influences the
ordering degree of pores. At a relatively low external tensile
stress, regular hexagonal arrangement of pores was observed.
However, a high tensile stress completely destroyed the pore
arrangement of porous AAO. Large holes and pits, rather than
nanopores, appeared on a highly stressed surface. This
experimental result revealed that the mutually repulsive
mechanical force between neighboring pores, which is
associated with volume expansion due to oxidation of the
metal, may be the driving force for the self-organized formation
of hexagonally close-packed arrangement of nanopores, as
suggested by Jessensky et al.165
As to the effects of compressive stress on pore growth, Park
et al.181 have performed the anodization of aluminum confined
in micrometer-sized vertical trench patterns. The authors
observed that during the anodization of the confined aluminum,
the anodization rate is significantly retarded at the vertical
sidewall of the trench. Because of the retarded anodization rate,
most of the aluminum at the edge part of the structure remains
and its thickness decreases gradually with increasing distance
from the vertical sidewall toward the central part of the trench
structure (Figure 21). The authors attributed this phenomenon
to the accumulation of compressive stress at the vertical
sidewall of the trench structure, where linear vertical volume
expansion is severely prohibited by additional stress. The Figure 22. (a) Cross-sectional SEM image of AAO nanopore formed
authors noted that because compressive stress is an additional by horizontal anodization. Scale bar = 100 nm. (b) Schematic
kinetic barrier to the electrochemical oxidation of aluminum, illustration of the formation mechanism of horizontal AAO with
the anodization kinetics of aluminum should be severely dendritic internal pore structure. Reproduced with permission from ref
retarded. 186. Copyright 2011 The Electrochemical Society.
S dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

Figure 23. Schematic diagram of the kinetics of porous AAO growth in (a) potentiostatic and (b) galvanostatic conditions: (a) Current (j)−time (t)
curves for potentiostatic anodization (i.e., U = constant) and (b) potential (U)−time (t) curve for galvanostatic anodization (i.e., j = constant).
direction is prohibited by traction at the insulating top layer, maximum due to the ready diffusion of electrolyte (stage III).
the extra volume of newly formed anodic alumina is extruded After that, current (j) reaches a steady value after passing
inside the primary pores, resulting in a dendritic structure, as through an overshoot (stage IV). The appearance of current
schematically illustrated in Figure 22b. overshoot has been related to the decrease of the initial pore
6.2. Initial-Stage Pore Formation density with the steady-state growth of major pores:168 pores
increase in size by persistent merging with adjacent pores. For a
6.2.1. Qualitative Description on Pore Formation. given set of anodization conditions, the rate of potential
Porous AAO can be easily fabricated by anodization of increase at the very beginning of anodization, the value of the
aluminum in acid electrolytes either under a constant potential minimum current, the time needed for anodizing current to
(i.e., potentiostatic) or a constant current (i.e., galvanostatic) reach a steady value, and the appearance of the current
condition. In general, potentiostatic anodization is widely overshoot have been known to be directly dependent on the
employed for the fabrication of self-ordered porous AAO, anodizing potential (U), electrolyte pH and temperature, and
because of the linear relation between the applied potential (U) the initial surface state of the aluminum.168,187,188
and the structural parameters of the resulting AAO (i.e., pore For the case of galvanostatic anodization, a similar
diameter Dp, interpore distance Dint, and barrier layer thickness progression can be observed for stages I−IV, while the
tb, section 5). Figure 23 shows (a) a typical current (j)−time (t) potential (U) changes as a function of time (Figure 23b).
curve for potentiostatic anodization, (b) potential (U)−time (t) Under constant-current conditions, the oxide growth rate
curve for galvanostatic anodization, together with (c) schematic should be proportional to the applied current density (j) and
illustrations of the stages of porous structure development.101 constant according to the Faraday’s law. In addition, a constant
When a constant anodic potential (U) is applied, a thin electric field (E = U/tb) is required to sustain the applied
compact barrier oxide starts to grow over the entire aluminum constant current (j).76 Accordingly, the potential (U) increases
surface (stage I). Thickening of the initial barrier oxide over with the thickness of the growing barrier oxide (tb), as shown in
time (t) results in an increase of the series resistance (R) of the the inset of Figure 23b. However, in practice, the evolution of
anodization circuit. Current (j) is initially maintained at the potential (U) deviates from a simple linear increase with time,
limiting current (jlimit) of the power supply, and correspond- as shown in Figure 23b. For convenience, various mechanisms
ingly potential (U = jR) increases linearly with time (t) (see the governing such a deviation have been referred to as growth
inset of Figure 23a). When the thickness (or the resistance, R) instabilities, which include, for example, mechanical breakdown
of the compact barrier oxide layer reaches a certain value, during zirconium anodization, and surface undulation/pore
current (j) drops rapidly to hit the minimum value (stage II). initiation during aluminum anodization.178 Figure 23b shows a
For this stage, O’Sullivan and Wood100 suggested that current gradual retardation of potential (U) increase at stage II. Such a
(i.e., electric field) concentrates on local imperfections (e.g., potential evolution can be attributed to a morphological
defects, impurity, pits) existing on the initial barrier oxide, instability, that is, transition from the stage of barrier oxide
resulting in non-uniform oxide thickening and pore initiation at growth to the stage of porous oxide growth.178 In the following
the thinner oxide areas. Thompson and co-workers10,33,44 have sections, we will discuss in detail the kinetics and morphological
proposed that local cracking of the initial barrier oxide due to instability involved in the early stage of anodization, which have
accumulated tensile stress (PBR < 1) may develop the paths for been systematically investigated by Proost and co-work-
electrolyte penetration. Local increase in field strength at the ers.160,175,178,189,190
penetration paths effectively polarizes the Al−O bonds, 6.2.2. Kinetics of Porosity Initiation. Recent publications
facilitating field-assisted oxide dissolution there (section have shown that the growth of a porous AAO and its self-
6.3.2),100 and eventually leads to development of individual organization are most likely driven by the internal stresses
penetration paths into embryo pores.10,44 Accordingly, further developing in the anodic oxide.47,190−192 Proost and co-workers
anodization leads to a gradual increase in current (j) to a local have investigated the initiation of porosity during galvanostatic
T dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
Figure 24. (a) Curvature change and cell voltage evolution as a function of anodization time at 5 mA cm−2 in 1 M H2SO4 (22 °C); (b) radial power
spectral density (PSD) of samples anodized for different times. Reprinted with permission from ref 190. Copyright 2009 AIP Publishing LLC.
anodization of aluminum thin film on a silicon substrate in 1 M (i.e., regime A). This implies that the oxide formation efficiency
sulfuric acid (22 °C) at j = 5.0 mA cm−2 by in situ monitoring (ηj) during the initiation of porosity is higher than that during
of the internal stress-induced curvature of the substrate.190 the initial barrier oxide formation, which is in line with the
They observed that the magnitude of the substrate curvature increase in the oxide growth rate upon pore initiation, as shown
(ΔK, in km−1) increases at a constant rate in the compressive by in situ monitoring of the internal stress-induced curvature of
direction up to a transition time (ca. 7.9 s) at which the rate of the substrate (vide supra).190 On the other hand, the authors
curvature change suddenly increases (Figure 24a). The attributed the lower Al3+ loss rate during the pore initiation
observed curvature transition was attributed to the initiation stage to the non-uniformity of current distribution upon
of porosity accompanied by an increase of the oxide growth commencement of pore initiation.189 In sulfuric acid, the Al3+
rate. This was confirmed by a quantitative analysis of the radial loss rate during stages II and III was constant, and increased
power spectral density (PSD) distributions of the anodized slightly at the beginning of stage IV. In phosphoric acid,
surfaces as presented in Figure 24b, in which the first (λ1) and however, the cation loss rate decreased again during stage II
second (λ2) correlation breaks are associated with the and then remained more or less constant during stages III and
aluminum grain morphology, and the appearance of porosity, IV (regime C). The authors associated the difference in the
respectively. Further, the authors pointed out that the increase observed evolution of Al3+ loss rate with the morphological
in growth rate after the curvature transition would not be differences of the growing anodic oxide (i.e., pore size and
expected if the porous layer grew by dissolution of the oxide at spacing).189 In sulfuric acid, the rate of Al3+ loss during the
the pore base.190 steady-state pore growth stage was similar to the level of the
Hoar and Yahalom76,187 have proposed that the pore barrier layer growth stage, whereas in phosphoric acid both
initiation occurs at a sufficiently low electric field due to rates were markedly different; there was a higher rate during the
proton entry into the initial barrier oxide at preferred sites, barrier layer growth stage. For both cases of anodization, the
where concentrated electric field (i.e., current) accelerates oxide rates of Al3+ loss were observed to linearly increase with the
dissolution to develop pores. The authors187,193 suggested that current density (j). Proost et al.189 suggested that the direct
the Al3+ ions found in the solution originated from the oxide at proportionality between the rate of Al3+ loss and the current
the pore base as a result of field-assisted (rather than “thermal”) density (j) can be attributed to the direct ejection of Al3+ ions
oxide dissolution (see section 6.3.2). Yet later studies29,30,161 into the electrolyte, because the field-assisted contribution may
have revealed that Al3+ ions in the electrolyte are the result of be relatively independent of the current density according to
direct ejection of Al3+ ions from the metal/oxide interface the high field conduction theory.25 For both cases of
through the oxide into the solution (see section 6.3.4), rather anodizations, the oxide formation efficiency (ηj) during the
than coming from the field-assisted oxide dissolution process. porous oxide growth stage was found to increase with current
Recently, Proost et al. have for the first time correlated the density (j). For phosphoric acid anodizing, however, the
kinetics of Al3+ loss to the morphological changes occurring efficiency (ηj) during the barrier oxide growth stage did not
during the very early stage of galvanostatic anodization of increase with current density (j), and remained constant in the
aluminum in 1 M sulfuric acid160 and 0.4 M phosphoric acid189 current range j = 2.0−10 mA cm−2 (Figure 25), which is
by employing in situ inductively coupled plasma optical different from the case of sulfuric acid anodizing.160 The
emission spectrometry (ICP-OES). For both anodization abnormal efficiency values at 1.0 mA cm−2 in Figure 25 were
cases, the authors observed three distinct regimes of Al3+ loss. suggested to occur when field-assisted dissolution (see section
However, the evolution of the Al3+ loss rate turned out to be 6.3.2) rather than direct cation ejection (see section 6.3.4)
markedly different, as follows. For the same current density, the becomes the predominant mechanism of Al3+ loss for current
rate of Al3+ loss is higher in phosphoric acid than in sulfuric acid densities lower than 2.0 mA cm−2.164,189
during the barrier layer growth stage (regime A, stage I in 6.2.3. Morphological Instability. As was briefly men-
Figure 23b). On the other hand, the Al3+ loss rate is lower tioned at the end of section 6.2.1, at the very early stage of
during the pore initiation stage (regime B, stage II in Figure anodization, pores initiate as a result of the morphological
23b), as compared to the barrier oxide layer formation stage instability of growing anodic oxide. This becomes evident at an
U dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
(i.e., potential vs time) was characterized by three well-defined

regimes, as discussed in the previous section. By converting the
curvature versus time curve (see Figure 24a) into a stress−
thickness versus potential curve, the authors obtained internal
stress data corresponding to the barrier layer growth regime
from the slope of the stress−thickness versus potential curve
(Figure 27). On the basis of the anodizing ratio (AR) of 1.1 nm
Figure 25. Dependence of the oxide formation efficiency (ηj) on

current density (j) for Al anodizing in 0.4 M H3PO4 during barrier
growth (regime A, i.e., stage I in Figure 23b, ■) and steady-state
porous growth (regime C, i.e., stages III−IV in Figure 23b, □).
Reproduced with permission from ref 189. Copyright 2011 The
Electrochemical Society.
Figure 27. (a) Stress−thickness versus cell potential curves during
oxide thickness of a few nanometers as shown in Figure galvanostatic anodization of aluminum for 20 s in 1.0 M H2SO4 (22
26.67,161,168,178,190,194 Previous research has suggested that °C) at 5 mA cm−2. The vertical dashed line indicates the moment of
pore initiation. (b) Oxide thickness at pore initiation versus
instantaneous internal stress in the barrier. The numbers near data
points indicate corresponding current density in mA cm−2. Reprinted
with permission from ref 178. Copyright 2011 Elsevier.
V−1 for aluminum anodizing in 1.0 M H2SO4, they then could

plot the thickness at pore initiation (the first vertical dashed
line in Figure 27a) as a function of stress for a set of anodizing
experiments performed at different current densities, j = 1.5−25
mA cm−2 (Figure 27b). It turned out that oxide thickness at the
point of pore initiation increases with the compressive stress.
The authors claimed that such a dependency revealed that
“pore initiation itself does not correspond to a stress-affected
instability, although further development of the instability into
an ordered steady-state pore morphology can be considered to
be stress-affected (i.e., porosity-induced stress relaxation).”178
Instead, as an alternative instability criterion, they suggested
that electrostatic energy acts as a driving force not only for
porosity initiation, but also for selection of the interpore
distance (Dint) of anodic oxides.175
More recently, Hebert and co-workers194 performed a linear
stability analysis of an instability mechanism controlled by oxide
dissolution and ionic migration at the initial stage of pore
formation. The authors claimed that previous mod-
els101,192,196−198 based on nonlinear interface kinetics may be
Figure 26. Cross-sectional TEM micrographs of anodic oxide film on unrealistic, because the oxide formation efficiency (ηj) is weakly
Al anodized in 0.4 M H3PO4 at 4.5 mA cm−2 for (a) 17 s, (b) 34 s, and dependent on the current density (j).199,200 Their model
(c) 55 s. Adapted with permission from ref 161. Copyright 2010 The predicted that the range of oxide formation efficiencies (ηj)
Electrochemical Society. producing pattern selection depends on the cation charge (z)
and PBR; patterns with a minimum pore spacing occur within a
internal stress may play a role in the growth instability of narrow range of the oxide formation efficiency (ηj = 65−70%
anodic oxides.64,65,75,192,195 Van Overmeer and Proost178 have for porous anodic alumina and 50−58% for anodic titania),
investigated the relation between the internal stress, the which occurs if z > 2. According to the model, the wavelength
morphological instability, and the pore initiation during the for the maximum disturbance growth rate is proportional to the
growth of porous AAO. They employed a high-resolution in thickness of anodic oxide, which quantitatively explains the
situ curvature measurement technique to monitor the internal proportionality of interpore distance (Dint) to anodizing
stress during anodization of a thin aluminum film on a silicon potential (U). This holds for both disordered and self-ordered
substrate in 1.0 M H2SO4 at 5 mA cm−2. The anodization curve porous AAOs, and also for diverse anodizing electrolytes.
V dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
6.3. Steady-State Pore Formation anodization. Hoar et al.187,193 suggested that the local oxide
6.3.1. Joule’s Heat-Induced Chemical Dissolution. For dissolution is assisted by the increased electric field (E) due to
steady-state pore growth, the movement rates of the metal/ the geometry of the pore base. The proposed model suffers
oxide interface and the oxide/electrolyte interface should be disadvantages, however, in that it does not specify the details
balanced, keeping the barrier layer thickness (tb) constant. It associated with field-assisted oxide dissolution and it adopts the
has long been believed that this balance is achieved by a idea that the outwardly migrating Al3+ ions contribute to the
dynamic equilibrium between the oxide formation at the metal/ oxide formation at the oxide/electrolyte interface, which
oxide interface and the removal of oxide at the oxide/ actually does not occur in the case of porous-type oxide
electrolyte interface.100,101,168,193 Joule’s heat-induced chemical growth (see section 6.3.4).29,30
dissolution of the barrier oxide by acid electrolyte has been O’Sullivan and Wood100 proposed a detailed physical
suggested.7,127,168,187,201 However, this thermal mechanism mechanism for field-assisted chemical dissolution of anodic
does not reasonably explain the dynamic balance of the oxide, and qualitatively explained the dependence of the porous
movement rates of the interfaces (i.e., the metal/oxide and morphology on anodizing conditions. They explained the field-
oxide/electrolyte interfaces), because the rate of chemical assisted oxide dissolution in terms of the effective polarization
dissolution is typically much lower than that of oxide formation of Al−O bonds in the lattice at the oxide electrolyte interface
even at an elevated temperature.29 Generated heat has been under the field (Figure 28).100 In this model, the electric field
considered to play a role in enlarging pores by assisting
dissolution of the pore wall oxide, resulting in truncated pore
channels.202 From the experimentally determined oxide
formation rate (372.5 nm/min) in 1.5 M H2SO4 (21 °C) at
20 mA cm−2 and the chemical dissolution rate (0.084 nm/min)
in the same electrolyte, Hunter and Fowle201 inferred that the
electrolyte condition at the pore base must locally change to the
equivalent of boiling of 5.10 M H2SO4 at 124 °C to satisfy the
required rate of chemical dissolution (i.e., 372.5 nm/min). On
the other hand, on the basis of their calculations of steady-state
temperature distribution, Nagayama and Tamura203 reported
that local temperature rise due to Joule heating under a
comparable anodization condition (i.e., 1.0 M H2SO4, 27 °C,
and j = 9.4 mA cm−2) is not more than ΔT = 0.07 °C. They
claimed that the high rate of local oxide dissolution should be
interpreted as a consequence of high electric field (E)
impressed on the barrier layer, as had been suggested by
Hoar and Mott.193 Recent in situ measurements of anode
temperature during anodizations in 0.3 M H2C2O4 at 40 V have
shown that the maximum temperature change is ΔT ≈ 1 °C, Figure 28. Schematics of field-assisted dissolution mechanism by
O’Sullivan and Wood: (a) before polarization, (b) after polarization,
which contradicts Joule’s heat-induced chemical dissolution of
(c) removal of Al3+ and O2− ions, and (d) remaining oxide. Adapted
anodic oxide at the pore base.204 with permission from ref 100. Copyright 1970 Royal Society
6.3.2. Field-Assisted Oxide Dissolution. Hoar and Mott Publishing.
proposed193 that the thickness of the barrier oxide layer is
maintained by the dynamic rate balance between the following
two processes occurring at the oxide electrolyte interface: (1)
the oxide formation by the reaction between O2− ions and Al3+ (E) across the barrier oxide can effectively polarize (i.e.,
ions migrated from the metal/oxide interface, as in the stretch) the Al−O bond along the applied field direction,
formation of barrier-type oxide, and (2) the oxide dissolution. lowering the effective activation energy for bond dissociation.
The authors assumed that oxide formation takes place both at Solvation of Al3+ ions by water molecules via activated complex
the metal/oxide interface and at the oxide/electrolyte interface, (i.e., Al(H2O)63+) and the removal of O2− ions by H3O+ ions as
as in the barrier-type oxide formation. In their model, oxide at H 2O are facilitated. Because the electric field (E) is
the oxide/electrolyte interface is decomposed to Al3+ and O2− concentrated on the pore base, the oxide dissolution rate is
ions. The resulting Al3+ ions go into the electrolyte. Meanwhile, the greatest there, and a dynamic equilibrium between the
O2− ions in contact with acid electrolyte become OH− and oxide formation and the oxide dissolution can be established.
move through the oxide to form new oxide at the metal/oxide This model has popularly been cited in the literature to explain
interface. The proton (H+) released by the oxide formation the growth and morphology of porous AAO.
reaction would then diffuse back to the electrolyte by proton Several models based on field-assisted oxide dissolution have
transfer between the lattice O2− ions. Since the oxide ions from been developed. In their theoretical modeling, Parkhutik and
the oxide/electrolyte interface are spread over a larger area at Shershulsky101 considered the three-dimensional (3D) distri-
the metal/oxide interface, the oxide dissolution occurs at a bution of electric field and current in the barrier oxide layer and
greater rate compared to oxide formation at the metal/oxide included the field-assisted dissolution at the oxide/electrolyte
interface. In other words, the net result of process (2) is the and oxide formation at the metal/oxide interface as boundary
progressive thinning of the barrier oxide layer due to the conditions to predict the steady-state pore morphology. Their
requirement of oxygen volume conservation in the oxide, which model predicted that the movement rate of the oxide/
is compensated by the oxide formation through process (1) to electrolyte interface by field-assisted dissolution is pH-depend-
keep the thickness of the barrier layer constant during ent and has an exponential dependence on the electric field (E).
W dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
The model also predicted a linear dependence of interpore

distance (Dint) on anodizing potential (U).
Thamida and Chang198 were also able to predict the linear
dependence of the interpore distance (Dint) on the anodizing
potential (U). They performed a perturbation analysis of the
equation describing the movements of the metal/oxide
interface by oxide formation, and oxide/electrolyte interface
by oxide dissolution, the rate of which was considered to be
governed by the local electric field. The electric field at both
interfaces was considered to be dependent on the shape or
topography of the interfaces. Their model predicted that the
ratio of pore diameter (Dp) to interpore distance (Dint) is a
factor independent of anodizing potential (U), but varies with
the electrolyte pH.198 Singh et al.192 have further put forward
previous models. The main element of their model is the
Butler−Volmer relation, which describes the exponential
dependence of the current on the overpotential and the
dependence of the activation energy of oxide dissolution
reaction on the Laplace pressure and the elastic stress within
anodic oxide.192,205 Their model predicted ordered hexagonal
pore arrays for a range of volume expansion factors close to the
one observed for ordered porous films.
Recently, Friedman et al.206 performed a systematic
experimental investigation to study the stability phase diagram
as a function of pH and anodizing potential (U) in an attempt Figure 29. (a,b) SEM images showing field-assisted dissolution of
to validate the above-mentioned theoretical models. By anodic oxide under an electric field (E): (a) before and (b) after re-
anodization of a planar preformed Al2O3 layer in a 5 wt % H3PO4
considering the discrepancies between the previous theoretical solution at 86 V for 49 min. Scale bar = 200 nm. (c) Changes in the
models and their experimental results, they concluded that the thickness of a planar preformed Al2O3 layer due to electric field- and
previous models must include an appropriate weighting factor time-dependent dissolution behavior in a 5 wt % H3PO4 solution.
to account for the oxide formation and dissolution mechanism Reprinted with permission from ref 207. Copyright 2011 Elsevier.
during the pore formation. The discrepancies may originate
from the fact that these models were based on pore formation barrier-type oxide films were first formed in sodium arsenate
by field-assisted oxide dissolution at the pore base. In fact, the (Na2HAsO4·7H2O) solution, and subsequently the resulting
field-assisted dissolution mechanism for steady-state pore samples were re-anodized in phosphoric acid under electric
formation has recently been rejected by several authors (see fields (i) below the threshold electric field (E*) reported by Oh
sections 6.3.4 and 6.3.5). and Thompson for the formation of incipient pores, (ii) close
For the initial stage of anodization, on the other hand, Oh to the threshold field to induce significant anodic oxidation of
and Thompson207 have recently reported direct experimental aluminum, and (iii) well above the threshold field. From
evidence of the impact of the electric field (E) on the oxide microscopic analyses of the arsenic and 18O contents, and the
dissolution rate and the existence of a threshold electric field pore morphologies and arsenic distribution in the resulting
(E*) for pore initiation. To assess the effect of an electric field anodic oxide films, it was found that the field-assisted oxide
(E) on the Al2O3 dissolution rate, the authors re-anodized a dissolution is mainly responsible for the formation of incipient
planar pre-formed Al2O3 layer (thickness h0 = 160 nm) on pores at oxide formation efficiency (ηj) = ∼20−30%, while
aluminum and investigated the evolution of thickness of the field-assisted flow of oxide materials is operative for the growth
preformed oxide layer as a function of time (Figure 29). The of major pores at oxide formation efficiency (ηj) = ∼57−
thickness of the planar barrier oxide was found to have 66%.208 The authors suggested that the preferential growth of
decreased from 160 to 131 nm after re-anodization in 5 wt % incipient pores locally increases the current density at the pore
H3PO4 at 86 V for 49 min, without changing the thickness of bases, which may influence the transport numbers of mobile
the aluminum (i.e., no anodic oxidation of aluminum). In ions, insertion of electrolyte-derived anionic species into the
addition, the dissolution rate of the barrier oxide of a fixed anodic oxide, and thus oxide viscosity.208
initial thickness was found to increase with electric field (E). 6.3.3. Average Field Model for Steady-State Pore
The results indicated that field-assisted oxide dissolution is Structure. As discussed in section 6.2.1, after the formation of
operative at the initial stage of anodization. On the basis of the incipient pores, some large incipient pores develop into major
invariance of the thickness of aluminum and the morphology of pores by increasing their size through persistent merging with
the metal/oxide interface, Oh and Thompson suggested that neighboring smaller incipient pores. As the anodization
the formation of the incipient pores is associated with field- proceeds, the growing major pores readjust their sizes and
induced instability at the oxide/electrolyte interface at spatial arrangement to establish equilibrium morphology (i.e.,
sufficiently high electric field. In a separate work, Skeldon hexagonally close-packed pore distribution). During this period,
and co-workers have reported confirming experimental results merging, dying, or even branching of the pores may occur. For
of field-assisted oxide dissolution at the initial stage of pore a given set of anodization conditions, the barrier layer thickness
formation during potentiostatic anodization of aluminum in (tb), pore size (Dp), and interpore distance (Dint, or cell size) in
phosphoric acid.208 In their study of pore initiation, the authors the equilibrium pore structure are mainly determined by the
employed immobile arsenic species as tracers. 18O-labeled anodizing potential (U). O’Sullivan and Wood suggested a so-
X dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
called “average field model” to explain the establishment of the would be enlarged in the lateral direction. Accordingly, for all
equilibrium structure of growing pores.100 The essence of the three cases in Figure 30, rearrangement of pores in conjunction
model is that field-assisted dissolution at the base of growing with the self-adjustment of pore size (Dp) and barrier layer
pores should occur to some different extents until the electric thickness (tb) would take place until the electric field (E) across
field (E) across the barrier layers eventually becomes the same the barrier layers of every pore approaches the average field.
for every pore, the condition under which pores of an 6.3.4. Direct Cation Ejection Mechanism. The average
equilibrium size grow at a constant rate, being determined by field model discussed above is based on the field-assisted oxide
the average field. The model can be qualitatively explained as dissolution.100 However, this dissolution mechanism alone does
follows. Figure 30 schematically shows three adjacent pores not adequately explain some of the experimental results, in
particular, that the quantity of Al3+ ions in the electrolyte after
anodization exceeds that of Al3+ ions originating from the
formation of the pores. On the basis of pore-filling experiments,
Takahashi and Nagayama reported that transport numbers for
Al3+ and O2− ions moving across the barrier layer are t+ = 0.4
and t− = 0.6, respectively.46 The result implies that both Al3+
and O2− ions migrate in anodic oxide, with 40% of the ionic
current carried by the Al3+ ions and the remainder by the O2−
ions, and further that about 40% of the Al3+ ions are lost into
the electrolyte without contributing to the porous oxide
formation. Considering the porosity (P ≈ 10%) of porous
AAO formed in typical anodization conditions,109 30% of Al3+
ions should be lost through a mechanism different from field-
assisted oxide dissolution, even if the latter is still operative.
Siejka and Ortega studied the pore formation mechanism by
Figure 30. Schematic representation of growing three adjacent pores employing 18O tracing techniques.30 They first formed a
(a, b, and c) with different pore sizes (Dp1, Dp2, and Dp3) and barrier compact base oxide film on aluminum in electrolyte enriched in
layer thicknesses (tb1, tb2, and tb3). R1, R2, and R3 are the radii of H218O and subsequently anodized the sample in H216O-
curvature of the metal/oxide interfaces of the respective pores. ω enriched H2SO4 electrolyte for pore formation. From the
(∼45.7°) is the angle subtended from the center of curvature to the nuclear microanalyses for 18O-isotope content and depth
pore bases. The red lines extending from the metal/oxide interface to distribution, the 18O tracer was found to be located at the
the oxide/electrolyte interface represent current lines. The regions film surface conserving its initial isotopic concentration (Figure
marked with “A” correspond to the area of unoxidized metal near the 31b), which was attributed to oxide decomposition inside the
concave ridges.
growing with different pore sizes (Dp1, Dp2, and Dp3) and
barrier layer thicknesses (tb1, tb2, and tb3). We assume that pore
(b) has the equilibrium dimension of a given set of anodization
conditions, in which tb2 and R2 are the equilibrium barrier layer
thickness and radius of curvature of the metal/oxide interface,
respectively. Although O’Sullivan and Wood assumed that the
barrier layer thickness (tb) and the angle (w = 45.7°) in a
potentiostatic anodization are constant irrespective of the pore
sizes (Dp), we suppose here that only w remains constant while
tb changes with Dp, which represents the real cases better. For Figure 31. Schematic diagrams illustrating findings of oxygen tracer
the three cases given in Figure 30, the electric field (E) across experiments for the growth of (a) barrier and (b) porous anodic films
the barrier layers is different, because at a given anodizing on aluminum. In each case, the anodizing is carried out first in
potential (U) the field (E) is inversely proportional to the electrolyte enriched in H218O and second in electrolyte enriched in
barrier layer thickness (i.e., E = U/tb). Accordingly, field- H216O. Adapted with permission from ref 32. Copyright 2006 The
assisted oxide dissolution at the pore base would occur to a Electrochemical Society.
greater extent for pore (a), as compared to pores (b) and (c),
while anodic oxidation of metal would take place to the same oxide and reincorporation of the released oxygen to form new
extent at the metal/oxide interface due to higher current oxide at the metal/oxide interface. 18O-tracer studies along with
density (j) according to eq 1, until Dp1, R1, and tb1 have reached the analyses of the components of ionic current (jtot) have
their equilibrium values (i.e., Dp2, R2, and tb2). For pore (c), on further revealed that the number of oxygen in porous AAO
the other hand, field-assisted oxide dissolution and anodic accounts for about 60% of the total ionic current (i.e., jox =
oxidation reactions would be progressively retarded because of 60%·jtot), which is numerically equal to the current efficiency
lower electric field (E), until pore (c) has the equilibrium (ηj) of porous AAO formation.29,30 The remainder is associated
dimension. Unoxidized metal near the hemispherical concave with the loss of Al3+ ions into the electrolyte (i.e., jloss = 40%·
ridges (i.e., the points marked with “A” in Figure 30) is acted jtot). Siejka and Ortega claimed that pore formation in the
upon by two lateral field components of different magnitudes absence of oxygen losses should be associated with the direct
from two neighboring pores. The lateral field component of ejection (jAl = 30%·jtot) of Al3+ ions from the metal/oxide
greater magnitude drives the field-assisted dissolution and interface into the electrolyte across the barrier oxide and the
anodic oxidation to a greater extent. The corresponding pore outward movement (jdec = 10%·jtot) of Al3+ ions produced by
Y dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
Figure 32. Cross-section transmission electron micrographs (TEM) of (a) the sputter-deposited aluminum containing a tungsten tracer layer, and
following anodization for (b) 180 s, (c) 240 s, and (d) 350 s at 5 mA cm−2 in 0.4 M H3PO4 at 293 K. Reprinted with permission from ref 98.
Copyright 2006 Elsevier. The distributions of tungsten tracer in anodic oxide are schematically illustrated above the respective TEM images. (e)
Simulated current lines and potential distribution for porous AAO growth in oxalic acid at 36 V (color scale is potential in volts). (f) Simulated flow
velocity vectors and mean stress (color scale is dimensionless stress). Panels (e) and (f) reproduced by permission from ref 200. Copyright
2009Macmillan Publishers Ltd.: Nature Materials.
oxide decomposition inside the barrier layer toward the immediately beneath the pores initially lies slightly below the
electrolyte: jloss = jAl + jdec = 40%·jtot.30 Consistent results adjacent tracer near cell wall regions (Figure 32b). Upward
have recently been reported by Skeldon and co-workers,161 who displacement of the tracer band at the cell wall regions became
observed that the amounts of 18O tracer species in films formed pronounced upon further anodizations, as compared to the
by sequential anodizing in phosphoric acid do not change tracer below the pores, where the band is getting fainter
significantly during the formation of anodic oxide between the because of a reduced tungsten concentration (Figure 32c,d). It
barrier and porous stages. The direct cation ejection was suggested that the fine-tungsten lines along the cell
mechanism is also in line with the recent report by Wu et al., boundaries beneath the tracer layer are associated with the
who have experimentally shown that the formation of pores tungsten enrichment in the aluminum adjacent to the
does not occur through oxide dissolution process at the oxide/ aluminum/film interface, because formation of WO3 requires
electrolyte interface, but through direct ejection of Al3+ ions higher Gibbs free energy as compared to Al2O3.98,212,213 The
into the electrolyte.31 However, the process involved in oxide authors pointed out that the observed behavior of the tracer
decomposition inside the barrier layer and its role in the band is contrary to what one would expect from the
dynamic balance between the movement rates of interfaces (i.e., conventional dissolution-based model of porous AAO growth
the metal/oxide and the oxide/electrolyte interfaces) need to as follows.32,98 According to the conventional model of pore
be specified. formation, tungsten tracer should be incorporated into the
6.3.5. Flow Model for Steady-State Pore Formation. anodic oxide first at the regions immediately below the pores
Skeldon et al.32,98,209,210 have investigated the development of and then near the cell boundary regions because of the
pores in porous AAO by performing tracer studies. They scalloped geometry of the barrier oxide layer. Thus, the tracer
anodized Al/W-tracer/Al substrates (W-tracer layer; 3−5 nm band at the pore regions should lie ahead of the tracer at the
thick, Al−30 at. % W, Figure 32a) in H3PO4 solution and pore wall regions because of the outward migration of tungsten
investigated the movement of the tracer band (WO3) by TEM species, contrary to the experimental observations. If field-
and RBS.32,98 During anodic oxidation, tungsten species assisted oxide dissolution occurred at the oxide/electrolyte
incorporated into the anodic oxide migrated toward the interface, to maintain a constant barrier layer thickness (tb), a
oxide/electrolyte interfaces at about 0.38 of the rate of Al3+ tungsten-rich layer with a sharp image contrast (instead of
ions.211 It was observed that the incorporated tracer band diminished contrast, as in Figure 32c) would have been
Z dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
observed by TEM at the pore bases due to preferential Skeldon and co-workers213,218 have also investigated the
dissolution of Al3+ ions of a higher mobility in anodic oxide. effect of the types of tracer elements on the distributions of
On the basis of the results of tracer experiments, Skeldon and tracer layers in anodic alumina. Figure 33 schematically
co-workers32,98 proposed the flow mechanism of pore
generation, as an alternative process to conventional field-
assisted oxide dissolution. According to the new model, the
constant thickness of the barrier layer (tb) during porous AAO
formation is maintained by viscous flow of oxide materials from
the pore base to the cell boundary. It was suggested by the
authors that the displacement of oxide materials is driven by
large compressive stresses (∼100 MPa) from electrostriction
due to a high electric field (E ≈ 106 V cm−1)97 and also by
volume expansion due to oxidation of aluminum,165 and that
can be facilitated by the involvement of most of the oxide
constituents in ionic transport (i.e., the plastic flow of oxide
materials).97,214,215
In most anodizations for porous AAO formation, acid anions
from electrolytes are incorporated into the barrier layer through
inward migration. They migrate slowly in the barrier oxide, as
compared to O2−/OH− ions, due to their relatively large size.
As a consequence, the barrier layer exhibits a duplex structure
in terms of chemical composition, with an acid anion
contaminated outer oxide layer and a relatively pure inner
oxide layer adjacent to the metal/oxide interface (see section Figure 33. Schematic diagram comparing (a) hafnium-, (b) neo-
5.2).14 The relative thickness of the outer oxide layer to the dymium-, and (c) tungsten-containing tracer layers in porous anodic
inner one depends mainly on the nature of the anodizing films formed on aluminum in phosphoric acid. Reprinted with
electrolyte in a given set of anodizations and is invariant permission from ref 213. Copyright 2009 Elsevier.
throughout anodization. The flow model accounts for
incorporation of electrolyte anions into anodic oxide and also
compares the distributions of hafnium-, neodymium-, and
their migration behavior in the barrier layer. Incorporated
tungsten-containing tracer layers in porous films formed in
anionic species are transported toward the cell walls in addition
phosphoric acid. Contrary to what was observed from the tracer
to their inward migration in the oxide without dissolution- studies using tungsten, the hafnium and neodymium exhibited
related loss; otherwise, the barrier oxide would eventually the types of movement behaviors that one might expect from
contain no incorporated acid anions because of their slow field-assisted oxide dissolution. The authors attributed the
migration. The flow model considers Al3+ ions as the only ionic observed behaviors of tracer bands to the fast movement rates
species being lost into the electrolyte by field-assisted direct of the tracer cations (i.e., Hf4+ and Nd3+) in anodic alumina as
ejection.30 Garcia-Vergara et al. have pointed out that bulky compared to W6+ ions and also to the loss of fast moving tracer
acid anions play a key role in the flow of oxide materials, cations into the electrolyte through direct ejection mechanism;
influencing not only the pore and cell dimensions but also the Hf4+ ions migrated outward in anodic alumina at about the
self-organization of pores through the redistribution of same rate as Al3+ ions,219 while Nd3+ ions migrated about twice
stress.32,98,216 The isotopic order and the absence of tracer as fast as Al3+ ions (i.e., 6 times faster than W6+ ions).220
loss in the earlier 18O tracer studies of Siejka and Ortega (see Although the authors’ explanation of the unexpected distortion
section 6.3.4)30 have also been recently reinterpreted in terms seems to be plausible within the present knowledge of
of the field-induced plastic flow of oxide materials from the anodization, more systematic experimental investigations
pore base toward the cell boundary, during which most of the using other electrolyte systems and theoretical study are
initially incorporated 18O tracers are displaced to the cell required to fully verify the oxide flow model.
walls.161 The formation of dendritic (or fish-bone-like) pores in
a mechanically constrained environment has also been 7. SELF-ORDERED POROUS ANODIC ALUMINUM
explained in the framework of the flow mechanism.186,217 OXIDE (AAO)
The flow mechanism of steady-state pore generation has Studies on porous-type anodization have been mainly led by
been supported by the theoretical modeling of Houser and the surface finishing industry, and hence focused on the
Hebert,47,199,200 which highlighted not only the ionic migration development of cost-effective anodizing processes and the
under the gradients of mechanical stress and electric potential, improvement of engineering properties of anodized products.
but also its implication on the Newtonian viscoelastic flow of Although various anodizing processes have been intensively
oxide materials from the pore base toward the pore bottoms explored by industry, the size uniformity and spatial ordering of
and further into the cell walls (see Figure 32e,f). Yet, the model pores have not been considered a major concern. Typical
does not take into account the volume expansion stress at the porous AAOs formed by industrial processes, represented by
metal/oxide interface for the viscous flow of the oxide materials. hard anodization (HA), exhibit disordered pore structures with
The authors concluded that the compressive stress at the pore numerous micrometer-sized cracks.221−224 Therefore, classical
base drives the flow of oxide materials in association with the HA processes have not been implemented in the current
competition of strong anion adsorption with deposition of nanotechnology research, until the recent development of new
oxygen ions.200 HA processes. On the other hand, the mild anodization (MA)
AA dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
Figure 34. (Left) A schematic showing a conventional two-step mild anodization (MA) process for self-ordered porous anodic aluminum oxide
(AAO): (i) the first long-term anodization, (ii) removal of disordered porous AAO, and (iii) the second anodization at the identical condition to the
first one. Representative surface SEM micrographs of the respective samples are shown in panels (a), (b), and (c), respectively. Reprinted with
permission from ref 228. Copyright 1998 Springer Science and Business Media. (d) A color-coded SEM image of AAO formed by two-step MA
using 0.3 M oxalic acid at 40 V, showing a poly-domain structure. An area with the same color consists of a domain. The pores are color-coded on
the basis of the average angle to the six nearest neighbors. Pores that have no apparent hexagonal coordination (i.e., defect pores) are marked with
white. Reprinted with permission from ref 226. Copyright 2008 The American Chemical Society.
of aluminum produces self-ordered porous AAOs with uniform aluminum substrate maintaining their directional coherency
pore size (Dp) and interpore distance (Dint), which can be easily (Figure 34c). Position-defined pore generation during the
tuned by an appropriate selection of anodization conditions. second anodization has been attributed to the relatively thin
Thus, that process has been intensively utilized in academic native oxide at the bottom of each concave, where the electric
research for a wide variety of nanotechnology applications. Yet field (E) is the highest and the resistance is the lowest.168 In
the MA process is slow (film growth rate = 2−10 μm h−1), and general, porous AAOs formed by two-step MA process exhibit a
can be conducted within a narrow range of anodizing polydomain structure (Figure 34d).226 The lateral size of the
conditions. In the following sections, we will discuss the defect-free domain increases with the anodizing time, but is
conventional MA and the newly developed HA processes, limited to several micrometers.
factors governing the structure of porous AAO, and some Since the development of the two-step process from oxalic
characteristics of porous AAO that are relevant to nano- acid-based anodization, a lot of studies have been conducted
technology applications. In addition, recent attempts to not only to produce porous AAOs with different pore sizes and
engineer the internal pore structure of AAO by pulse densities with an improved arrangement of pores, but also to
anodization (PA) and cyclic anodization (CA) will be understand the mechanism responsible for the growth and self-
discussed. organizing behavior of pores during anodization. Particular
7.1. Mild Anodization (MA) efforts have been devoted to exploring the optimum conditions
Masuda and Fukuda found that the bottom part of porous for pore ordering, mainly with sulfuric, oxalic, or phosphoric
AAOs films produced by anodizing of aluminum in 0.3 M oxalic acid. Studies have indicated that the self-organized growth of
acid at 40 V exhibits a self-ordered pore structure as a result of ordered pores occurs within a relatively narrow window
the gradual rearrangement of the initially disordered pores.5 On (known as the “self-ordering regime”) of anodizing conditions
the basis of this experimental finding, Masuda and Satoh (see Figure 36). For a given electrolyte system, in the case of
developed the so-called “two-step anodization” process, by MA, there is an optimum anodizing potential (U) for the best
which porous AAOs could be obtained with a highly ordered ordering of pores: (i) sulfuric acid (0.3 M H2SO4) at U = 25 V
106,227
arrangement of uniform nanopores (Figure 34).6 In a typical for an interpore distance (DMAint ) = 65 nm; (ii) oxalic acid
two-step anodization, the first anodization process is conducted (0.3 M H2C2O4) at 40 V for Dint = 103 nm;6,106,168,227,228 (iii)
MA
11
for more than 24 h. The resulting porous AAO with disordered selenic acid (0.3 M H2SeO4) at 48 V for DMA int = 112 nm; and
MA
pores in its top part (Figure 34a) is selectively removed by the (iv) phosphoric acid (0.3 M H3PO4) at 195 V for Dint = 500
so-called “PC-etching” process using an aqueous mixture of 0.5 nm.109,229 Considerable efforts have been made to explore new
M H3PO4 and 0.2 M CrO3 at 80 °C.225 The surface of the self-ordering regimes in a wider range of DMAint . With the idea of
resulting aluminum is textured with arrays of almost hemi- controlling self-organization by adjusting the mechanical stress
spherical concaves (Figure 34b). The second anodization is between the metal/oxide interface, Shingubara et al. employed
carried out with the textured aluminum under the same a mixture solution of 0.3 M sulfuric acid and 0.3 M oxalic acid
condition employed for the first anodizing. Pores nucleate at (v/v = 1:1) to change the density of the resulting porous AAO
the centers of each concave feature and grow normal to the and obtained self-ordered porous AAO with DMA int = 73 nm at U
AB dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

= 37 V.230 More recently, Sun and co-workers231 reported an demonstrated fabrication of porous AAOs with pore diameter
H3PO4-based MA process using aluminum oxalate ((Al- less than 15 nm by using an aqueous mixture of sulfuric acid
C2O4)2C2O4) as an additive to suppress breakdown of porous and ethylene glycol (EG).234 Chen et al. noted two possible
AAO during anodization at high potential and temperature. origins for the decreasing porosity with the addition of organic
They showed that the interpore distance (DMA int ) of porous additive:233 (i) the increase of the effective electric field (E) due
AAOs can be continuously tuned from 410 to 530 nm by to the reduction of the dielectric constant (ε) of the anodizing
performing anodization with the mixture solution at an electrolyte upon addition of an organic modulator, and (ii) the
anodization potential (U) ranging from 180 to 230 V. Ono weak chemical dissolution of the pore wall oxide under the
et al.17,232 demonstrated the fabrication of porous AAOs with protection of organic molecules. Among them, the former is in
an interpore distance range of 300−600 nm by MA in organic line with the earlier report by Ono et al. that the Dp/Dint ratio
acid electrolytes: DMA int = 300 nm for 5 M malonic acid at 120 V, decreases with increasing electric field strength (E) during
DMA
int = 500 nm for 3 M tartaric acid at 195 V, and Dint = 600
MA anodization.232 Su et al. have further explored the effect of
nm for 2 M citric acid at 240 V. Yet the spatial ordering and size electric field (E) on porosity (P). In a series of papers,235−237
uniformity of pores of the resulting porous AAOs were by far they proposed a mechanistic model, proposing that the porosity
inferior to those formed by conventional MA processes using (P) of AAO is directly governed by the relative rate of water
sulfuric, oxalic, or phosphoric acid, which would limit the dissociation at the oxide/electrolyte interface, according to the
practical applications of such porous AAOs to nanotechnology following relation:236
research.
P = 3/(n + 3) (66)
For self-ordered porous AAO formed by MA processes,
recent morphological studies indicated that anodizing potential where n is the amount of water that dissociates per mole of
(U) determines the interpore distance DMA int , barrier layer Al2O3 in the oxide dissolution reaction given in reaction 15.
MA 106,109,116
thickness tMA b , and pore diameter Dp . The interpore The model regards both the dissociation of water and the
distance (DMA int ) and barrier layer thickness (tMA
b ) increase dissolution of oxide at the oxide/electrolyte interface as
linearly with anodizing potential (U) with proportionality important processes, although the latter has recently been
constants ζMA = 2.5 nm V−1 for DMA int and ARMA = 1.2 nm V
−1
largely disputed, as discussed in sections 6.3.4 and 6.3.5. By
106,109,114
for tMA
b . The observed potential dependence of D MA
int performing quantum-chemical model computations, the
and tMA b is consistent with the earlier reports for disordered authors showed that the electric field (E) can significantly
porous AAO.7,100,114 Linear dependence of the pore diameter facilitate heterolytic dissociation of properly oriented water
(DMAp ) on anodizing potential (U) has also been reported both molecules at the oxide surface, that is, field-enhanced water
for disordered and for self-ordered porous AAOs. O’Sullivan dissociation.41 Under a stronger electric field (E), the
and Wood100 reported that pore diameter of disordered AAOs dissociation rate of water will be increased (i.e., an increase
increases with anodizing potential at a rate of ζp = 1.29 nm V−1. of the n value in eq 66), and thus the porosity will be reduced.
For self-ordered porous AAO, on the other hand, Nielsch et As such, the model appears to adequately explain the
al.109 proposed that self-ordering of pores requires a porosity dependence of porosity (P) on electric field (E). The above
(PMA) of about 10% regardless of the specific anodizing relation was derived from a simple geometric consideration of
−1
conditions by assuming DMA int = 2.5 nm V . Because porosity growing AAO and the mass balance of total oxide-forming
(PMA) of AAO is given by eq 53, 10% porosity requirement of oxygen anions produced by the dissociation of water and
Nielsch et al. dictates a linear increase of the pore diameter with dissolution of Al2O3. In other words, the original model by Su
the anodizing potential at a late of ζp = 0.83 nm V−1, et al. postulates that all of the oxygen anions produced by water
irrespective of anodizing conditions. However, there are a dissociation and oxide dissolution should contribute to the
number of recent reports, indicating that the self-ordering of oxide formation at the metal/oxide interface.236 However, by
pores can occur at other porosity (PMA) values ranging from itself this assumption does not fulfill the necessary condition
0.8% to 30% depending on the MA conditions, and thus that required for the formation of the steady-state pore morphology,
the anodizing potential (U) is not the only parameter that is, the constant barrier layer thickness (tb) maintained by
determining the pore diameter (Dp).11,102,232,233 For example, the dynamic balance of the movement rates of metal/oxide and
Nishinaga et al. have recently reported fabrication of porous oxide/electrolyte interface, as follows. A close inspection of
AAO with DMA MA
p = 10.4 nm and Dint = 112 nm (porosity, PMA = reaction 15 used in the authors’ model reveals there is a
0.8% according to eq 53) by H2SeO4-based anodization at 48 V different field dependence for the water dissociation than for
and 0 °C.11 The authors noted that the solubility of anodizing the oxide dissolution process. To increase the n value under a
acid electrolyte has important effects on pore diameter and stronger electric field (E), water dissociation should occur at a
interpore distance, and suggested that the weak solubility of greater rate than oxide dissolution. Under such circumstances,
selenic acid under the anodization condition employed caused one may expect a progressive increase of the barrier oxide layer
the formation of 10-nm-scale pores.11 In another example, thickness (tb) as the anodiziation proceeds. Therefore, other
Chen et al. reported a continuous decrease of the pore ionic processes may be required to explain the constant
diameter, which did not affect either the interpore distance or thickness of the barrier layer during anodization. It was
the barrier layer thickness, when increasing the concentration of assumed that Al3+ ions are directly ejected from the metal/
polyethylenglycol (PEG) additive in phosphoric acid electro- oxide interface without contributing to the oxide formation.235
lyte.233 Because the porosity (P) of AAO is determined by the When MA is conducted outside the self-ordering regime, the
ratio of the pore diameter to the interpore distance (i.e., Dp/ degree of spatial ordering of nanopores decreases drastically.
Dint in eq 53), increasing the PEG concentration in the For a given acid electrolyte, there is a breakdown potential
anodizing electrolyte corresponds to decreasing the porosity of (UB), above which anodization is accompanied by local
AAO. The use of an organic additive to reduce the pore thickening, burning, and cracking of the anodic oxide film,
diameter has recently been extended by Martiń et al., who caused by a catastrophic flow of current (j) and consequent
AC dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
evolution of a large amount of heat:4,18,79,89,94,97,238,239 UB = 27,

50, and 197 V for sulfuric, oxalic, and phosphoric acid,
respectively. It has been known for the MA process that
anodizations just below the breakdown potentials (UB) yield
porous AAOs with the best self-ordered pore structures.18 Ono
and co-workers232,240 investigated the self-ordering of nano-
pores at the local areas of burnt protrusions with a large
number of cracks. They found that the locally thickened areas
formed by breakdown exhibit domains of highly ordered cell
arrangement. In addition, the cell size (Dint) and the barrier
layer thickness (tb) of porous AAO at the burnt area were
observed to be remarkably smaller than those at the burnt-free
area, which is in line with the earlier report by Tu et al.239
These experimental observations imply that current density (j)
primarily determines the degree of spatial ordering of pores and
the structural parameters (i.e., cell size Dint and the barrier layer
thickness tb) of porous AAOs.
7.2. Hard Anodization (HA)
As mentioned in section 4.1, stable anodization in a given Figure 35. (a,b) SEM images showing weak cell junction strength of
electrolyte is difficult to maintain over breakdown potential porous AAOs formed by H2SO4-hard anodization (HA). (c) A
(UB) due to the occurrence of burning or breakdown of the schematic illustration showing two different fracture modes of porous
AAOs formed by H2SO4-hard (HA) and mild anodization (MA): the
growing anodic oxide film. Classical hard anodization (HA)
A−A′ cleavage plane for HA-AAO and the B−B′ cleavage plane for
processes adopted in industry have typically been conducted at MA-AAO. Panel (a) reprinted with permission from ref 18. Copyright
potentials (U) higher than breakdown value (UB) at the 2006 The Electrochemical Society. Panel (b) reprinted with
expense of randomly occurring local breakdown of anodic oxide permission from ref 113. Copyright 2008 The American Chemical
film. The processes take advantage of high speed growth Society.
(typically 50−100 μm h−1) of oxide films due to the high
current density (j) at an increased anodizing potential (U). process exhibited poor mechanical stability, which greatly limits
However, the resulting porous anodic films are characterized by their practical application as templates for various nano-
severely buckled (or uneven) surfaces with numerous cracks fabrications. The produced porous AAOs exhibited weak cell
and non-uniform (or distorted) pores. Control of the pore size junction strength (Figure 35a), and thus the individual alumina
(Dp), interpore distance (Dint), and the aspect ratio of the nanotubes could be easily separated upon applying a weak
nanopores is also very difficult. For these reasons, the classical external stress (Figure 35b), unlike the case of porous AAOs
HA processes have not been employed for nanotechnology formed by MA processes (Figure 35c). Chu et al. pointed out
applications. that the concentration of Al3+ ions dissolved in an aged solution
Various attempts have been made to overcome the problems plays a key role in the stable growth of porous AAOs at high
associated with local breakdown events during HA. The potentials (U > Ub) and current densities (j), avoiding the
research activity to date includes extending anodizing potential burning or breakdown of porous AAO films.18,110 However, the
(U) over breakdown potentials (UB) by appropriately tuning electrochemical action of the aged solution has not yet been
the three major pore-forming acid electrolytes (i.e., H2SO4, clearly understood. In an attempt to determine the effect of
H2C2O4, and H3PO4), by searching for new anodizing aged solutions on breakdown potential (UB), Schwirn et
electrolytes, and by efficiently removing the reaction heat. al.113,119 performed a series of HA experiments at the potential
The current density (j) in HA process is typically 1 or 2 orders range of U = 27−80 V by using sulfuric acid containing
of magnitude higher than that of conventional MA processes. different concentrations of Al3+ ions. Their results have shown
Thus, Joule’s heating (Q) during HA is 2 or 4 orders of that stable anodization at high potentials (U > UB) is actually
magnitude greater than the ordinary MA processes. The determined by the initial limiting current density (jlimit), not by
excessive heat during the HA process can not only promote the solution state.
acidic dissolution of the resulting porous AAO, but also trigger For an oxalic acid-based anodization system, Lee et al.111
local breakdown events.4,239 have shown that the self-ordering regimes can be extended by
Chu and co-workers18,110 reported that the breakdown performing HA of aluminum. By introducing a thin (ca. 400
potential (UB = 27 V) in a sulfuric acid-based anodization nm) porous oxide layer onto an aluminum substrate, gradually
system can be increased up to 70 V by experimentally aging the increasing the anodizing potential (U) to a target value (100−
electrolyte after a long-term anodizing (i.e., pre-electrolyzing) 160 V) at the rate of 0.5−0.9 V s−1, and effectively removing
at 10−20 A hours per liter. Because of the high anodizing the reaction heat through direct thermal contact of the
potential (U), the current density (j) for stable anodization aluminum substrate with an underlying cooling plate, the
correspondingly rose significantly, and thus led to a high-speed authors could suppress the breakdown of oxide films and grow
film growth. The authors were able to fabricate self-ordered mechanically stable highly ordered porous AAOs at anodizing
porous AAOs with Dint = 90−130 nm at 40−70 V and 160− potentials of U > 100 V. Their HA process established a new
200 mA cm−2 at 0.1−10 °C. That condition is far from those of self-ordering regime with widely tunable interpore distances:
MA (H2SO4: 25 V and 2−15 mA cm−2) but similar to those of DHA
int = 220−300 nm at U = 110−150 V and j = 30−250 mA
classical HA,221,223,241−243 although the authors named this cm−2. They suggested that current density j (i.e., the electric
process “high-field anodization”. Porous AAOs formed by this field E) is a key parameter governing the self-ordering of pores
AD dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
agent for lowering the freezing point of the electrolyte down to

−10 °C, but also as a coolant for removing a large amount of
reaction heat through its vaporization from the metal/oxide
interface. The process allowed the fabrication of self-ordered
porous AAOs with various interpore distances: DHA int = 70−140
nm for H2SO4-HA at 30−80 V, 225−450 nm for H2C2O4-HA
at 100−180 V, and 320−380 nm for H3PO4-HA at 195 V.118,122
Microscopic investigations of HA-AAOs have shown that the
barrier layer thickness (tb) increases at a rate of ARHA = 0.6−1.0
nm V−1 with respect to anodizing potential (U) depending on
the current density (j),18,111,113,118,119 which is smaller than
ARMA ≈ 1.2 nm V−1 for MA-AAOs.7,100,114 Lee et al.111
attributed the reduced ARHA (i.e., anodizing ratio) to the high
current density (j) involved in the HA process in accordance
with the high field conductivity theory, which predicts an
inversely proportional dependence of tb to the logarithm of
current density (j) at a given anodization potential (U) (see eq
1). Figure 36 summarizes the self-ordering potentials (U) and
corresponding interpore distances (Dint) of porous AAOs
formed by MA and HA in three major pore-forming
electrolytes (i.e., H2SO4, H2C2O4, and H3PO4). It was found
that HA-AAOs exhibit a reduced potential (U) dependence of
the interpore distance (Dint) with a proportionality constant
ζHA = 1.8−2.1 nm V−1,16,110,111,113,118,122,244,245 as compared to
self-ordered MA-AAOs (i.e., ζMA = 2.5 nm V−1).109 On the
other hand, HA experiments performed at potentiostatic
Figure 36. (a−f) Representative SEM images of MA- and HA-AAOs. conditions (i.e., U = constant) have also shown that the
Panel (a) reproduced with permission from ref 226. Copyright 2008 interpore distance (DHA int ) of HA-AAOs decreases with the
The American Chemical Society. Panel (b) reproduced with current density (j), indicating that anodizing potential (U) is
permission from ref 106. Copyright 1998 AIP Publishing LLC. not the only parameter determining the cell size of porous
Panel (c) reproduced with permission from ref 229. Copyright 1998 AAOs.16,111,113,118 Lee et al. assumed that high mechanical
The Japan Society of Applied Physics. Panel (d) reprinted with stress at the metal/oxide interface due to high current density j
permission from ref 110. Copyright 2005 Wiley-VCH Verlag & Co.
(i.e., high electric field strength, E) may be responsible for the
KGaA, Weinheim. Panel (e) reproduced with permission from ref 111.
Copyright 2006 Nature Publishing Group. Panel (f) reproduced with reduced ζHA.111 In other words, energetically unfavorable field-
permission from ref 118. Copyright 2006 IOP Publishing. Reprinted induced mechanical stress (i.e., electrostriction pressure) was
with permission from IOP Publishing. (g) Self-ordering regimes in MA suggested to be accommodated by reducing the cell size to
(filled symbols) and HA (open symbols) by using H2SO4 (black increase the surface area of the metal/oxide interface. This is
symbols), H2C2O4 (red symbols), H2SeO4 (green symbol), and reminiscent of the decrease of critical wavelength (λc) of surface
H3PO4 (blue symbols). The black solid lines represent the linear undulations upon increase in the internal stress (σ) for an
regressions of the data with correlation parameters of ζMA = 2.5 nm initially flat surface (i.e., λc → ∞ as σ → 0) according to the
V−1 and ζHA = 1.8−2.0 nm V−1. Data for H3PO4-HA (△) show model of Srolovitz:246,247
current density (j) dependence of the interpore distance (Dint) at a
fixed anodizing potential (U = 195 V). Data derived from refs 106,227 λc = πMγ /σ 2 (67)
for H2SO4-MA, refs 5,106,168 for H2C2O4-MA, ref 11 for H2SeO4, refs
109,229 for H3PO4-MA, ref 113 for H2SO4-HA, ref 111 for H2C2O4- where γ is the surface energy and M is the biaxial modulus of a
HA, and ref 118 for H3PO4-HA. solid. On the other hand, on the basis of the experimentally
observed tensile to compressive stress transition during
at a given anodizing potential (U), which is in line with the galvanostatic anodization in 0.4 M H3PO4, Proost et al. have
suggestion by Ono et al.232,240 The authors also found that HA reported that the factor controlling the interpore distance (Dint)
process produces porous AAOs at 25−35 times faster growth is not likely to be an internal stress-induced surface
rates, as compared to conventional MA processes. Interestingly, perturbation, but rather an electrostatic energy-induced surface
the porosity (PHA) of HA-AAOs was found to be 3.3−3.4%, instability with the critical perturbation wavelength (λc) given
which is about one-third of the porosity value (PMA ≈ 10%) by the following equation:175
that was proposed as a requirement for self-ordered MA-AAOs
by Nielsch et al.109 The experimental method has also been λc = (4πtbγ /ε0εrE2)1/2 (68)
applied to sulfuric and malonic acid-based HAs.16,113
As mentioned above, HA of aluminum is accompanied by a where tb is the barrier layer thickness, ε0 and εr are the vacuum
large amount of reaction heat. Accordingly, the reaction heat and the relative permittivities of the oxide, respectively, and E is
should be properly removed for stable anodization at high the electric field.248 The instability equation predicts that the
potential (U > UB) and current density (j). To this end, Li et interpore distance (Dint) is a function of (tb/E2)1/2 with the
al.118,122 added ethanol (C2H5OH) to the aqueous anodizing slope of 2π/(γ/ε0εr)1/2. Interpore distances measured during
electrolytes (e.g., H2SO4, H2C2O4, and H3PO4) and conducted the growth of porous anodic alumina and titania agree closely
stable HA at high potentials (U) and current densities (j). In with those predicted by their electrostatic energy-based
their HA processes, the added ethanol served not only as an perturbation criterion.175
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Figure 37. (a) Current (j)−time (t) transient showing spontaneous current (j) oscillation during hard anodization of aluminum at 200 V with an
unstirred 0.3 M oxalic acid. An instant solution agitation was introduced at the time indicated by the arrow in (a). (b) An enlarged j−t curve after the
electrolyte agitation, together with the corresponding pore structure of AAO. Reprinted with permission from ref 103. Copyright 2010 Wiley-VCH
Verlag GmbH & Co. KGaA, Weinheim.
Recently, Lee et al.103 accidently found that porous AAOs current density (j) during anodization of aluminum under
that experienced spontaneous current oscillations (amplitude potentiostatic conditions.
∼800 mA cm−2) during a potentiostatic HA under unstirred 7.3. Pulse Anodization (PA)
electrolyte conditions exhibit modulated pore structures. From
anodizing experiments performed at potential (U) = 140−200 Ordered porous AAOs with tailor-made internal pore structures
V, the authors observed that peak profiles of the oscillating may provide a new degree of freedom in templated syntheses of
novel nanomaterials,249−251 and also serve as ideal platforms for
currents are symmetrically sinusoidal with relatively small but
investigating the adsorption and separation behaviors of diverse
increasing amplitudes at the early stage, while asymmetric with
particles, ions, or biologically important molecules.252−254 On
larger and uniform amplitudes at the lager stage of anodization
the basis of the experimental finding that HA of aluminum
(Figure 37a). The oscillation period was observed to increase produces porous AAOs with one-third lower porosity (P) than
with time. Microscopic investigation of the resulting porous MA (i.e., PHA ≈ 3% for HA and PMA ≈ 10% for MA), Lee and
AAOs revealed that the pattern of pore modulations matches co-workers111 have demonstrated fabrication of AAOs having
exactly with the detailed profile of oscillating current peaks periodically modulated nanopore diameters along the pore axes
(Figure 37b); the pore diameter and the segment length of by combining MA and HA processes (Figure 38). In their
modulated pores increase with the amplitude and the period of method, each step for modulation of pore diameter (Dp)
oscillating currents, respectively. The authors attributed the required a tedious manual exchange of the anodizing
spontaneous current oscillations to the periodic concentration electrolytes to satisfy both MA and HA conditions. In an
change of anodizing electrolyte at the pore bottom under attempt to avoid this problem, they have recently developed an
unstirred electrolyte (i.e., a diffusion-controlled anodic approach for continuous modulations of internal pore structure
oxidation of aluminum). On the basis of the observed of porous AAOs by pulse anodization (PA) of aluminum under
dependence of the pore diameter on the anodizing current a potentiostatic condition using sulfuric or oxalic acid
density, they suggested that the internal pore structures of solution.112 Historically, pulse anodization (PA) of aluminum
porous AAOs can be tailored by judiciously controlling the was developed in the early 1960s.255,256 The process has
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Figure 38. SEM image of porous AAO with modulated pore diameters prepared by cycling mild anodization (MA) and hard anodization (HA). A
magnified image of the area marked with a white rectangle is shown as an inset. Reproduced with permission from ref 111. Copyright 2006 Nature
Publishing Group.
popularly been employed in the aluminum industry to produce

anodic films of high technical quality (i.e., improved corrosion
and abrasion resistance) at an efficient rate of produc-
tion.257−259 However, the process has been out of view in
academic research in the past four decades, and has not been
applied to the development of nanostructured materials due to
the non-uniform and disordered pore structures of the resulting
anodic alumina.
In a newly developed PA process, a low potential (UMA) and
a high potential (UHA) are alternately pulsed to achieve MA and
HA conditions, respectively. A typical pulse profile is
schematically shown in Figure 39. A current recovery behavior
is observed for MA pulses, similarly to the current evolution at
the early stage of ordinary MA processes (Figure 23a). Current
is high at the initial stage, drops to a minimum value, and then
gradually increases to reach a steady value after passing an
overshoot.112,260,261 On the other hand, upon applying an HA
pulse, the current density (j) increases steeply (typically, jHA ≈
10−102 × jMA) for a short period of time and then decreases
exponentially, which is the typical anodization kinetics of HA of
aluminum under a continuous potentiostatic condition.111 In
the anodization of aluminum, Joule’s heat (Q) for a given Figure 39. Schematics showing potential (U)−current (j) relation
during potentiostatic pulse anodization (PA).
period of time (t) is proportional to the square of the current
density (j):
of the Joule’s heat. The heat generated by an HA-pulsing can be
Q = Ujt = R bj 2 t (69) effectively dispersed during the subsequent MA-pulsing.224,263
In a typical PA process, the current density (j) changes
where Rb is the resistance of the barrier layer.262 HA of periodically to the values determined by pulsed potentials (i.e.,
aluminum produces a large amount of reaction heat due to the jMA for UMA and jHA for UHA; jMA < jHA). As a consequence, the
high anodic current density (j). The generated heat would resulting porous AAO exhibits a lamellar structure with
increase the proton activity of the acid electrolyte, and thus may alternate stacking of MA-AAO slab with a smaller pore
cause undesired acidic dissolution of pore wall oxide or even diameter and HA-AAO slab with a larger pore diameter
local burning of the growing porous AAO via catastrophic local (Figure 40a−c), where the thickness of each oxide layer is
flow of current (i.e., electrolytic breakdown). Therefore, the determined by the pulse durations (i.e., τMA for MA-pulse and
heat should be properly removed during anodization at high τHA for HA-pulse).112,224 In addition to such a structural
current density (j). PA provides an effective way of dissipation modulation, porous AAOs formed by PA also exhibit a periodic
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Figure 40. (a) Scheme for the preparation of porous AAOs with modulated pore diameters by pulse anodization (PA). (b) False-colored SEM image
of AAO formed by H2SO4 PA. AAO slabs formed by MA and HA pulses are indicated by MA-AAO and HA-AAO, respectively. (c) SEM image
showing modulated pore diameter. (d) SEM image of 3D stacks of MA-AAO slabs, obtained by selective removal of HA-AAO slabs by chemical
etching. Reproduced with permission from ref 112. Copyright 2008 Nature Publishing Group.
compositional modulation along the pore axes. TEM-EDX ultrasonic treatment to separated individual nanotubes from the
point analysis of porous AAO formed by sulfuric acid-based PA sample.
revealed that the amount of anionic impurities (mostly SO2− 4 ) As was discussed in section 7.2, MA and HA exhibit different
in HA-AAO slabs is about 88% higher than that in MA-AAO dependences of the barrier layer thickness (tb) on anodizing
slabs, which was attributed to the high current density (jHA) potential (U); ARMA ≈ 1.2 nm V−1 for MA and ARHA = 0.6−1.0
during HA-pulsing.112 As discussed in section 5.2, anodic oxide nm V−1 for HA. According to eq 1, the anodizing current
contaminated with anionic impurities exhibits a poor chemical density (j) is exponentially proportional to the inverse of the
stability against an oxide etchant (e.g., 5 wt % H3PO4). By barrier layer thickness (tb). In PA of aluminum, therefore, when
taking advantage of higher level of anionic impurities in HA- the anodizing potential is changed from a higher UHA to a lower
AAO slabs, Lee et al.112 could completely separate the MA- UMA, the current density drops abruptly from jHA to a minimum
AAO slabs from a single as-prepared porous AAO by value and then increases gradually to a value (jMA) determined
performing selective chemical etching of HA-AAO slabs (Figure by UMA (i.e., current recovery). It was reported that the time
required for a complete recovery of anodizing current depends
40d).
on the chemical nature of the barrier oxide (i.e., the content of
Structural modulation of porous AAOs can also be achived
anionic impurities), the electrolyte temperature, and the
by galvanostatic PA, where current pulses satisfying MA and
potential difference between UHA and UMA.112,264 For PA in
HA conditions are periodically applied. As discussed in section three major pore-forming acid electrolytes, Lee and Kim noted
7.2, H2SO4-AAO formed under HA conditions shows fairly that the time required for current recovery increases in the
weak junction strength between cells.110,112,113 On the basis of order: H2SO4 < H2C2O4 < H3PO4.264 Further, they pointed out
this experimental finding, Lee and co-workers263 explored a that PA of aluminum in H2C2O4 or H3PO4 electrolyte is
convenient route for the mass preparation of uniform alumina difficult to achieve continuously within a reasonable period of
nanotubes with prescribed lengths. The authors applied time because of the retarded current recovery, especially at a
periodically galvanic MA and HA pulses to achieve continuous low temperature and a large potential difference.264 To resolve
modulations of pore diameter and also to weaken the junction the problem associated with the slow current recovery, they
strength between cells. Alumina nanotubes, the length of which increased gradually anodizing potential prior to pulsing a high
is determined by the HA-pulse duration (τHA), could be anodizing potential.264 Porous AAOs with tailor-made internal
obtained by immersing the resulting porous AAO into an pore geometries could be conveniently prepared by employing
aqueous mixture of 0.2 M CuCl2 and 6.1 M HCl, followed by potential pulses with deliberately designed periods and
AH dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
Figure 41. Schematics showing (a) the experimental process for the fabrication of AAO with tailor-made pore structures by pulse anodization (PA)
and (b) a generalized form of a potential pulse employed in pulse anodizations. Uj and τij define the repeating unit of potential waves, where Uj = the
potential at the time tj with U1 = U5 (j = 1−4), τij = tj+1 − tj, i = the pulse number (i = 1, 2, 3...). Representative SEM image of porous AAOs with
modulated pores prepared by pulse anodization; (c) τ11 = 36 s, (d) τ11 = 144 s, (e) τ11 = τ21 = 36 s, τ31 = τ41 = 144 s, and (f) τ11 = τ21 = 144 s, τ31 =
36 s, τ41 = 144 s, τ51 = τ61 = 36 s. Other parameters were fixed at U1 = 80 V, U2 = 140 V, U3 = U4 = 160 V, τi2 = τi4 = 0 s, τi3 = 0.2 s. The repeating
units of pulses are shown as insets in the respective images. Reprinted with permission from ref 264. Copyright 2010 IOP Publishing.
amplitudes (Figure 41). This capability for engineering internal beginning with first cycle having a gradually increasing
pore geometry may provide a unique opportunity in templated amplitude of current, then a double-profiled cycle, and last a
synthesis of nanowires and nanotubes with modulated series of triangular galvanic cycles.265 AAOs with periodically
diameters, and also in utilization of porous AAOs with 3D perforated pores (i.e., pores with nanoholes along horizontal
periodic pore structures in photonic applications. directions) were also fabricated by chemical etching of cyclic
7.4. Cyclic Anodization (CA) anodized porous AAOs.266
The concept of structural engineering of porous AAO by 7.5. Anodization of Thin Aluminum Films Deposited on
Substrates
combining MA and HA has been put forward by Losic et
al.,265,266 who developed a new anodizing process, called cyclic In addition to overcoming their brittle characteristics, AAOs
anodization (CA). They employed periodically oscillating grown with thin Al films deposited on substrates of choice
current signals with different cyclic parameters (i.e., period, would potentially offer much broader application than those on
amplitude, and profile) during anodization of aluminum to bulk aluminum foils. The substrate could be insulators (e.g.,
achieve structural modulations in porous AAOs (Figure 42).265 glass),267−270 semiconductors (Si and TiN),271−277 non-valve-
Porous AAOs with modulated pores of different shapes metal (e.g., Cu, Ag, Au, Pt, etc.)270,278−283 or valve-metal (e.g.,
(circular- or ratchet-type), diameters, and lengths were Ti, W, Nb, Zr, Ta, etc.)-coated Si substrates,284−290 and
prepared by applying current signals of deliberately chosen transparent indium thin oxide (ITO).291−298 AAOs formed by
cyclic parameters. Microscopic investigation of AAOs formed anodizing thin Al films on substrates have been utilized not
by CA processes indicated that the structural details of pores only as patterning masks, but also as templates for fabricating
follow exactly the applied current profiles. The authors pointed various functional nanostructures, including arrays of Si
out that the transitional anodization (TA) mode, the transition nanoholes,271 carbon nanotubes (CNT),287 magnetic nano-
from MA to HA condition (Figure 42d), is important for wires,289,293 thermoelectric nanowires,270 photocatalytic nano-
structural engineering of pores in CA process. It was proposed wires or nanotubes,293,296 and valve-metal oxide nanodots or
that the TA mode creates a pore, whose internal geometry is nanorods.277,284,286,288
directed by the characteristics (i.e., profile, period, and Previous works have indicated that the anodizing behavior of
amplitude) of the applied cyclic signal. They further showed the interfacial area of the Al and substrate material depends on
nanostructuring of porous AAOs with distinctive, hierarchical the underlying material in terms of anodization kinetics and
internal pore structures by employing multiprofiled current structure of the barrier layer (Figure 43). When anodizing Al
signals: for example, three different successive CA steps, films on insulating substrates (e.g., SiO2) in three major pore-
AI dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
Figure 42. (a) Schematics of the galvanostatic cyclic anodization (CA) for structural modulation of porous AAO. (b,c) SEM images of AAOs with
modulated pores fabricated by asymmetrical current signals (i.e., exponential saw-tooth) with two different amplitudes. (d) Influence of current
amplitude on the pore shape and the length of modulated pore segments. Anodization modes (i.e., MA, TA, HA) associated with corresponding
anodization currents are marked on the pore structures and graphs. Reprinted with permission from ref 265. Copyright 2009 Wiley-VCH Verlag
GmbH & Co. KGaA, Weinheim.
Figure 43. Schematic current (j)−time (t) curves during anodization of thin Al films on (a) insulating substrates, (b) non-valve-metal-coated (or
ITO) substrates, and (c) valve-metal-coated substrates. (d−f) Schematic cross-sections of the respective porous AAOs. The solid curve in (b)
corresponds to j−t curve during anodization of silicon substrate without conducting surface layer.
forming electrolytes (i.e., H2SO4, H2C2O4, and H3PO4, Figure Nb, Zr, Ta, etc.) are filled with corresponding oxide nanodots
43a,d), the completion of the anodization is marked by a sharp or nanorods, protruding from the barrier layer (Figure
decrease in current density (j) and color change.267−270 The 43c,f).284−290
barrier layer has a U-shaped morphology like that of AAO Among the above-mentioned substrate materials, the
formed from bulk Al foils. Al just underneath the cell boundary anodization of Al film on a Si substrate has been the most
remains unoxidized in the form of discrete nanometer-sized extensively investigated. When anodizing an Al/Si substrate,
particles, which are trapped between the alumina barrier layer after the complete anodization of the Al film, oxidation of the Si
and the insulating substrate. Unlike bulk Al foils, however, the surface forms SiO2 nanodots under an inverted barrier oxide
barrier layers of AAOs formed by anodization of Al films on layer. The thickness of the inverted barrier layer is significantly
conductor-coated substrates (e.g., Si, Pt, Au, ITO, etc.) are reduced as compared to that formed on bulk Al
characterized by inverted morphology with interfacial voids foils.271,272,299,300 Seo et al. suggested that formation of
(Figure 43b,e).270−274,276−282,291−297 On the other hand, pores interfacial voids and the inversion of the barrier layer has a
of AAOs formed on valve-metal-coated substrates (e.g., Ti, W, mechanical origin, involving multiple process stages, as follows
AJ dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
Figure 44. Cross-sectional SEM images (top) and a schematic (bottom) showing the process of void formation: (a) touching of the barrier layer
with Si surface, (b) flattening of pore bottoms due to stress accumulation, (c) void nucleation to minimize the stress, and (d) formation of inverted
barrier layer. SEM images were adapted with permission from ref 276. Copyright 2007 Elsevier.
(Figure 44).276 When the barrier layer touches the Si surface, isotropic nature of anodic alumina etching. Moreover, several
the residual Al underneath the cell boundary region is laterally minutes of anodization of the sample resulted in detachment of
confined and thus cannot accommodate the volume expansion the AAO from the substrate surface. Yang et al. anodized an Al/
stress due to the rigid Si substrate without interfacial Au/Si substrate in an effort to circumvent the need to open the
restructuring to create the necessary additional space (i.e., barrier layer.281 Yet, the Al/Au bilayer system formed Au−Al
void). The driving force for void nucleation is the stress intermetallic phases, which catalyzed a deleterious oxygen
pushing the Si substrate downward. On the other hand, upward evolution reaction, causing detachment of the AAO membrane
stresses are exerted on the bottom of each pore, resulting in the from the substrate.281,283 For anodization of Al/Pt/Si
inversion of the barrier layer curvature (i.e., detachment of the substrates, a barrier layer thinning process based on stepwise
barrier layer). The electric field for anodizing the remaining Al voltage reduction279 or the use of a reverse bias in KOH270
is locally concentrated on the pore edges. As a result, a have been employed to minimize pore widening. However, the
dendritic branching occurs at the edge of each pore bottom. stepwise voltage reduction process resulted in the bifurcation of
The upward stress increases due to void growth during pores near the barrier layer. Under the reverse polarization
anodizing of the residual Al. The inversion behavior allows the conditions, the Pt underlayer catalyzed the electrolysis of water,
barrier layer to be farther away from the Si substrate, which violently evolving H2 gas and thus delaminating porous AAO
relieves the stress burden while the barrier layer becomes from the substrate. To improve physical bonding between the
thinner upon further anodizing.276 From TEM nanoprobe porous AAO and a conductor-coated substrate, a thin interlayer
energy dispersive X-ray spectroscopy (EDS), Seo et al.276 found (typically, ca. 5-nm-thick Ti) between the Al and the conductor
that the inverted barrier layer surrounding a void has a layer has been introduced.282,283,301 Yasui et al. introduced a
compositional bilayer structure with a thin Al-rich region near thin layer of Ti (1.5 nm) between the Al and Pt layer to serve
the void and relatively thick Al-poor region near the pore both as an adhesion promoter and as a barrier eliminating thin
bottom, the origin of which is likely to be associated with the TiO2 in 5 wt % H3PO4.282 Oh and Thompson have successfully
detachment process of the barrier layer during void formation. demonstrated a selective barrier perforation process by
Anodizing Al film/Si substrate for an extended period of time anodizing Al films on a W(60 nm)/Ti(15 nm)-coated silicon
results in a local oxidation of Si by electrolyte infiltrating substrate.289,290 Their process is based on selective dissolution
through the channels between the pore bottoms and voids, of the anodized valve-metal oxide (i.e., WO3) in a pH 7
forming SiO2 nanodots just underneath the voids,276,300 phosphate buffer solution. During removal of the WO3,
accompanied by a violent evolution of oxygen gas bubbles. isotropic pore wall etching did not take place due to the
As a result of the gas evolution, the porous AAO typically neutral nature of the etching solution. After the selective
delaminates from the Si substrate. Similar phenomena have also removal of WO3 from the pore base, Oh and Thompson could
been observed for anodization of Al films on ITO/glass directly grow Ni or Pt nanowires by electrodeposition into the
substrates, although Chu et al.291,292,295,298 have successfully pores of AAO, in which the exposed base metal layers served as
anodized thin Al films on ITO/glass substrate. This may be cathode.289,290
ascribed to improved physical bonding of the AAO as a result Pringle215 first theoretically analyzed the anodizing behaviors
of the sputter deposition of highly energetic Al atoms on the of superimposed valve-metal layers (i.e., bilayered metal films).
ITO/glass substrate. In the case of Al films on non-valve-metal- He predicted that the metal order would be conserved if the
coated substrates (e.g., Cu, Pd−Au, Ag, Pt), prolonged anodic oxide of the superimposed metal was less resistive, while
anodization results in detrimental breakdown or dissolution the metal order would be partially inverted through finger
of metal during the anodization.270 Accordingly, anodization for penetration of oxide by the underlying anodic oxide if the
a prescribed time is required for each substrate. superimposed anodic oxide was more resistive. He also pointed
For electronic applications, it is desirable to grow a barrier- out that these phenomena may be changed by the effects of
layer-free AAO directly on conductor-coated substrates. Sander transport number, relative rate of cation migrations, oxide
and Tan demonstrated the fabrication of a barrier-layer-free structure, and PBR.215 Later, this model was experimentally
AAO membrane by anodizing Al film deposited on an Au- confirmed by Shimizu and co-workers,214,302−304 who observed
coated substrate, followed by chemical etching of the barrier that the random penetrations of lanceolate oxide fingers from
layer in 5 wt % H3PO4.278 Yet their chemical etching process the less resistive underlying oxide layer into the more resistive
resulted in enlargement of the pore diameter, due to the upper oxide layer take place. Recent works by Mozalev and co-
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Figure 45. SEM images of anodic tantala nanorods formed by multi-step anodization of Al/Ta/Si substrate: (a) before and (b) after removal of
AAO. (c−e) Schematic cross-sectional views of (c) the Al/Ta bilayer anodized at 53 V in 0.2 M H2C2O4, (d) after potentiostatic re-anodizing from
53 to 310 V in 0.5 M H3BO3, and (e) after pore widening followed by re-anodizing from 53 to 310 V in 0.5 M H3BO3. Reprinted with permission
from ref 307. Copyright 2004 The Electrochemical Society.
workers have indicated that in certain electrolytes, anodizing of stamp (mold) onto the aluminum by mechanical pressure (i.e.,
thin Al deposited on a layer of valve-metals (e.g., W, Ti, Ta, nanoimprinting), followed by anodization. The SiC imprint
Nb) results in the filling of AAO pores with nanodots or stamps were fabricated with an array of convex features of
nanorods of the corresponding metal oxides (Figure desired arrangements in a limited dimension by electron beam
45).20,286,305−307 More recently, Chu et al.288 obtained similar lithography (EBL) technique.308−311 Each shallow indentation
experimental results from anodization of Al film on a Zr-coated formed on the aluminum surface defined the position of pore
glass substrate. Mozalev et al.307 pointed out that the filling of growth by initiating pore nucleation at the initial stage of
AAO pores with other valve-metal oxides is possible due to the anodization, and thus led to a perfect arrangement of pores
higher PBR and cation transport number (t+), as compared to within the patterned area (Figure 46a). Masuda et al. further
those of Al; for example, the PBR for Ta/Ta2O5 = 2.5 and t+Ta extended the method to fabricate pore array architectures with
= 0.24−0.5. square- or triangle-shaped pore openings in square or triangular
arrangements (Figure 46c,d).309 In a pre-pattern on aluminum,
8. LONG-RANGE ORDERED POROUS AAO the missing sites of the pattern can be compensated
Porous AAOs formed under the self-ordering conditions exhibit automatically during anodization, if the distance between the
a poly-domain structure, where each domain contains missing site and the nearest patterned sites satisfies the
hexagonally ordered nanopores of an identical orientation potential (U)−interpore distance (Dint) relation required for
and is separated by the boundaries. The domain boundaries are the self-ordering of pores (i.e., ζMA = Dint/U = 2.5 nm V−1,
characterized by defect pores (white dots in Figure 34d). For section 7.1).311 The size of the pores formed at those missing
most nanotechnology applications, porous AAOs with uniform sites is smaller than that of pores formed at the patterned sites
pore size and long-range ordering of pores are required. (Figure 46e,f). By utilizing this self-compensation ability in
Masuda et al.308 first reported fabrication of ideally ordered AAO growth, Smith and co-workers have demonstrated the
porous AAOs with a single-domain configuration over a few fabrication of porous AAOs with hybrid circular-diamond and
mm2 area. The process involved pre-patterning of the circular-triangular-diamond pore cross-sections.312 By anodiz-
aluminum surface by transferring the pattern of a hard SiC ing aluminum with surface pre-patterns in nonequilibrium
AL dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
Figure 46. (a) Schematics showing process for ideally ordered porous AAO. (b−d) SEM micrographs of porous AAOs with different hole array
architectures: (b) circular, (c) square, and (d) triangular pore openings. (e−j) SEM micrographs showing self-compensated pore formation; (e−g)
surface prepatterns with missing sites of pattern and (h−j) the respective porous AAOs formed by anodization. The black arrows in (h) indicate
pores formed at the missing sites of pattern in (e). SEM micrographs shown in (f,g,i,j) highlight formation of porous AAOs with (f,i) hybrid circular-
diamond and (g,j) hybrid cicular-diamond-triangle pore cross-sections; the scale bars are 500 nm. Panel (b) was reprinted with permission from ref
308. Copyright 1997 AIP Publishing LLC. Panels (c,d) were reprinted with permission from ref 309. Copyright 2001 Wiley-VCH Verlag GmbH &
Co. KGaA, Weinheim. Panels (e,h) were reprinted with permission from ref 311. Copyright 2001 AIP Publishing LLC. Panels (f,g,i,j) were reprinted
with permission from ref 312. Copyright 2008 AIP Publishing LLC.
tessellation arrangement (Figure 46f,g), the authors found that cracking the underlying brittle substrate, high mechanical
the cell geometries in the resulting porous AAOs are pressure also causes structural damage of the imprint stamp
determined by the arrangements of the unpatterned and after several times of pattern transfer.
patterned pore sites and also direct the cross-sectional shape of In attempts to resolve the above-mentioned problems, other
pores: circular, diamond, and triangular pores, respectively, in pre-patterning techniques have been proposed: evaporation of
regular, elongated, and partially compressed hexagonal cells thin aluminum film on ordered arrays of self-assembled Fe2O3
(Figure 46i,j). The authors attributed the evolution of diamond nanoparticles (NPs) on silicon followed by mechanical
and triangular pore cross-sections to a coupled effect between striping,318 resist-assisted or direct patterning by focused-ion-
the thick pore wall oxide and the longer segment length of cell- beam (FIB) lithography,319,328−330 and direct nanoindentation
boundary bands (section 5.2), suppressing or eliminating the using a tip of a scanning probe microscope (SPM).320,331 Yet
influence of the smaller cell segments.312 Porous AAOs with these methods are not practical for pre-patterning over an
sharp-featured non-circular pore cross-sections can be used as extended area due to the limited ordered area (ca. 2 μm2) of
templates in synthesizing functional nanostructures for nanoparticles for the first technique, and due to the serial
enhanced sensing in localized surface plasmon resonance nature of the patterning process for the other two techniques.
(LSPR) and surface-enhanced Raman spectroscopy (SERS).313 For large-scale fabrications of long-range ordered porous AAOs
Stimulated by the works of Masuda and co-workers, several on fragile substrates, pre-patterning of thin aluminum films by
groups have developed various surface pre-patterning methods holographic lithography,321 block-copolymer lithography,322
to fabricate single-domain AAOs with tunable interpore and nanosphere lithography (NSL)323 has been developed.
distances, Dint (Table 2). Earlier research in this direction was Fabrication of single domain porous AAOs over 2-in. silicon
mostly devoted to the development of an economic way of wafer has been also realized by directly anodizing thin
producing hard imprint stamps with large lateral dimensions. aluminum films deposited on a lithographically generated
Surface pre-patterning by mechanical nanoindentations using SiO2 mask, in which ordered SiO2 holes underneath the
optical diffraction grating,314 Si3N4 mold fabricated by deep-UV aluminum film define the position of pore growth by effectively
lithography,315 wafer-scale Ni mold fabricated by laser guiding the electric field during anodization.332 Most of these
interference lithography (LIL),317 and self-assembled mono- techniques have demonstrated their effectiveness in fabrications
or multi-layer of nanospheres316,327 is effective in terms of of ideally ordered porous AAOs with tunable interpore distance
process cost and pre-patterning area. However, these (Dint) on brittle substrates over an extended dimension.
approaches have an intrinsic limitation, in that they rely on However, they are inherently incapable of generating multiple
the transfer of stamp patterns onto the aluminum surface under copies of surface pre-patterns on aluminum.
high mechanical pressure (typically, 5−100 kN cm−2) and Soft lithography utilizing elastomeric poly-dimethylsiloxane
therefore are not suited for pre-patterning of thin aluminum (PDMS) stamp or nanoimprint lithography (NIL) on
layers deposited on technologically more relevant substrates for polymeric resist has been demonstrated as a versatile method
device integration, such as fragile silicon or glass. In general, as for multiple transfers of a master pattern onto various
the pattern density on an imprint stamp increases, the higher substrates.325,333,334 Pattern transfer in these lithographic
the required applied pressure must be in this pattern transfer techniques can be achieved at pressures 103−105 times less
protocol. In addition to severely deforming the aluminum and than those used in hard stamping directly onto aluminum. Lai
AM dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
Table 2. Methods of Surface Pre-patterning of Aluminum for Ideally Ordered Porous Anodic Aluminum Oxide (AAO)
reported
Al film on min Dint
pre-patterning methods substratea patterned area (nm) remarks refs
SiC stamp X 3 mm × 3 mm 63 SiC imprint stamp was fabricated using electron beam lithography (EBL); stamping pressure: 28 kN cm−2 308,310
optical diffraction grating X 5 mm × 5 mm 481 Al surface was pre-patterned by a two-step press-in procedure of optical diffraction grating 314
Chemical Reviews
Si3N4 stamp X 4-in. wafer 500 stamp with arrays of Si3N4 pyramids was replicated from a silicon master; stamping pressure: 5 kN cm−2 315
nanosphere crystals X >cm2 area 150 hexagonal array pattern of self-assembled nanosphere crystal was transferred onto Al surface; stamping pressure: 98 kN cm−2 316
Ni stamp X wafer scale 200 Ni imprint stamps were replicated from master patterns, fabricated by laser interference lithography (LIL); stamping pressure: 5−25 kN cm−2 317
Fe2O3 nanoparticles X 2 μm × 2 μm 13 6-μm-thick Al was deposited on self-assembled 2D arrays of Fe2O3 NPs on Si, and separated by using an adhesive tape for anodization 318
(NPs)
focused-ion-beam (FIB) O 100 pre-patterning of Al surface was achieved by focused Ga+-ion beam 319
lithography
probe-tip-based direct O 1 μm × 1 μm 100 the surface of Al was directly patterned by nanoindentation using the tip of a scanning probe microscope (SPM); indentation load: 40 μN 320
patterning
holographic lithography O 1 cm × 1 cm ∼300 thin Al films with periodic surface undulations were generated by depositing Al onto the photoresist-grating-patterns, developed by holographic 321
lithography
block-copolymer O 45 highly ordered hole array pattern of thin block copolymer film was transferred to the Al surface by reactive ion etching (RIE) 322
lithography
nanosphere lithography O >1 mm2 area 84 pre-patterning of Al film on a substrate was achieved by chemical etching of Al through the mask formed by sputter-deposition of tungsten on the 323
(NSL) ordered arrays of polystyrene sphere
mold-assisted chemical O 2 cm × 2 cm 277 pre-patterning of Al was achieved by contacting with Al etchant-absorbed PDMS mold 324
etching
2
nanoimprint lithography O ∼10 cm area 100 Ni mold was replicated from a master pattern fabricated by EBL, and its pattern was transferred onto a thermoplastic resist; subsequently, the resulting 325
(NIL) resist pattern was transferred onto an Al surface by Ar-ion beam milling; imprint pressure: 0.5 kN cm−2
AN
step and flash imprint O wafer scale 100 ordered arrays of nanoindents were generated by wet-etching of Al through pre-patterned polymer masks that were created by SFIL on Al surface; 326
lithography (SFIL) imprint pressure: <10−3 kN cm−2
a
Pre-patterning capability of thin Al film deposited on fragile substrates.
Review
dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

Figure 47. (a) Schematic diagrams showing fabrication procedures of ideally ordered porous AAO. (b−e) SEM images of porous AAOs fabricated
by the procedures shown in (a): (b) an overview image, (c) an image showing clear distinction between the pre-patterned (left) and non-patterned
(right) pore arrangement, (d) an SEM image of porous AAO with square arrangement of pores, and (e) a cross-sectional image of porous AAO
grown on silicon wafer. (f) A photograph of AAO template on a 4-in. silicon wafer. Panels (a−f) were reproduced with permission from ref 326.
Copyright 2010 The American Chemical Society.
Figure 48. (a) Cross-sectional SEM image of porous AAO formed by anodization of pre-patterned aluminum at an outside self-ordering condition:
pattern interval = 200 nm, anodization at U = 80 V using 0.04 M H2C2O4 (17 °C). (b) Dependence of the depth of ordered pores on the anodizing
potential (U): pattern intervals = 70, 100, 150, 200, and 250 nm for U = 28, 40, 60, 80, and 100 V, respectively. Anodizing electrolyte = 0.3 M
H2C2O4 for U = 28, 40, 60 V and 0.04 M H2C2O4 for U = 80 and 100 V. Reproduced with permission from ref 335. Copyright 2001 The
Electrochemical Society.
et al.324 reported a generic method of pre-patterning of an fabrication of single-domain porous AAOs with arbitrary
aluminum surface by mold-assisted chemical etching. Their interpore distances (Dint) and different pore lattice config-
technique is based on the reaction-diffusion wet-stamping (RD- uration on 4-in. silicon wafer (Figure 47).326 Their approach is
WETS) process, which creates ordered arrays of shallow etch based on the step and flash imprint lithography (SFIL) using a
pits on aluminum by the absorption/liberation of aluminum patterned quartz template. The SFIL was employed to pattern a
etchant adsorbed in a PDMS stamp. Single-domain porous polymer mask layer on aluminum film. Pre-patterning of the
AAOs with a square lattice configuration over 2 × 2 cm2 area aluminum surface was achieved by transferring the pattern of
were fabricated by anodization of the patterned aluminum. the polymer mask onto the underlying aluminum films by wet-
Recently, Kustandi and co-workers have demonstrated chemical etching. The authors claimed that the demonstrated
AO dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
Figure 49. General scheme for electrochemical deposition (ECD) of materials into porous AAO.
process provides significant merits over existing surface pre- interested readers to excellent recent review articles given in
patterning approaches in terms of patterning area, process refs313 and 336, that extensively cover the templated synthesis
simplicity, robustness, and throughput, allowing up to 10 000 and assembly of low-dimensional nanostructures and their
times of pattern transfers to the surface of aluminum films applications. As discussed in previous sections, self-ordered
deposited on fragile substrates.326 porous AAOs with tightly controlled pore size, density, and
As discussed above, anodization of pre-patterned aluminum intervals can be obtained by anodizing aluminum substrate
is indeed an effective way for obtaining ideally ordered porous under proper conditions. This provides many unique
AAO. It should be noted, however, that there is a major opportunities in the templated synthesis of low-dimensional
limitation of the process; to maintain the initially ideally functional nanostructures, allowing simple and cost-effective
ordered pore configuration, the obtainable maximum aspect preparations of extended arrays of structurally well-defined and
ratio of uniform nanopores depends critically on the identical nanostructures and also overcoming many of the
anodization conditions. For anodization of aluminum of a drawbacks of conventional state-of-the-art lithographic techni-
given pattern interval, one should properly select anodizing ques. During the last two decades, by taking advantage of its
parameters (e.g., potential and electrolyte) to fulfill the self- highly ordered structural feature, porous AAO has intensively
ordering requirement of pores. As discussed in section 7, for utilized as a template, stencil mask, or scaffold for functional
MA and HA using three major pore-forming acid electrolytes, nanostructures or nanodevices. The approaches employed for
there are specific ranges of anodizing potential (U), which give developing functional nanostructures include electrochemical
self-ordered pore structure. Under other applied potentials, the deposition (ECD), atomic layer deposition (ALD), chemical
depth of nanopores is limited in terms of ideal ordering (see vapor deposition (CVD), physical vapor deposition (PVD),
Figure 48).335 sol−gel deposition, surface modifications with technologically
important (bio)molecules, polymers or nanoparticles, melt
9. AAO TEMPLATE-BASED SYNTHESIS OF impregnation of materials, reactive ion etching (RIE), etc. A
FUNCTIONAL NANOSTRUCTURES vast variety of nanostructures including carbon nanotubes
(CNTs), metal, semiconductor, or polymer nanowires/nano-
While nanostructured materials are considered to have huge tubes, and ordered arrays of nanodots/nanoholes on various
application potential, cost-effective, high-throughput, and substrates have been successfully fabricated by utilizing porous
reproducible synthetic strategies are an essential prerequisite. AAO as a template or stencil mask. Their structure−properties
The synthesis of both simple and complex low-dimensional and functionalizations have been intensively investigated in an
nanostructures (e.g., nanodots, wires, tubes, core/shell NPs, attempt to utilize them for practical applications in safety,
organic−inorganic nanohybrids, etc.) relies largely on tem- energy, information, and biomedicine. In this section, we
plates, whose size, structure, and physicochemical properties are discuss AAO template-based synthesis of low-dimensional
predefined. Templated synthesis provides robust ways of nanomaterials, their functionalizations, and applications.
precise control over the size, shape and configuration, and
growth direction and place of otherwise unattainable nano- 9.1. Electrochemical Deposition (ECD)
structured materials. More importantly, it may also offer Possin337 implemented first the electrochemical deposition
opportunities for the in situ assembly of discrete nanostructures (ECD) of metal into a track-etched mica template to obtain 40-
(i.e., building blocks) into a well-defined hierarchical nm-thick and 15-μm-long Sn, In, and Zn nanowires. The
architecture for practical device applications. In principle, template approach was drawn a renewed attention by the works
almost all existing synthetic approaches and their combination of Martin and co-workers and has been popularly employed as
can be applied to the templated synthesis of nanostructured a nanofabrication strategy.338−342 The electrochemical deposi-
functional materials. Templates can be any substance with tion of materials into the pores of AAO template provides
nanostructured features, including DNA, protein, viruses, living marked advantages over other preparation methods of
organisms, colloidal nanoparticles, nanowires, nanotubes, block nanowires or nanotubes. In comparison to other deposition
copolymers, porous materials, etc.; the present authors refer techniques, such as chemical vapor deposition (CVD), atomic
AP dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
Figure 50. Scheme of the nanodisk code method. (a) Synthesis and functionalization. (b) Thirteen possible 5-disk-pair nanodisk codes with the
corresponding binary codes. (c) SEM images of Au/Ni multisegmented nanorods before (top) and after (bottom) deposition of the backing layer
and Ni etching. (d) Two-dimensional (top) and three-dimensional (middle) scanning Raman microscopy images of a 11111 nanodisk code.
Representative Raman spectrum of methylene blue (bottom) taken from the center of the hot spot generated in the middle disk pair shown in the
Raman maps above. Panels (a,b,d) were adapted from ref 358 with permission. Copyright 2007 The American Chemical Society. Panel (c)
reproduced with permission from ref 359. Copyright 2009Macmillan Publishers Ltd.: Nature Protocols.
layer deposition (ALD), and physical vapor deposition (PVD), focus our discussion on multisegmented metallic nanowires
the electrochemical deposition into porous templates is simple consisting of two or more different materials because of their
and inexpensive, and can be conducted without any special versatilities in terms of degree of freedom in functionalization
equipment. for various applications.
In general, to synthesize nanowires, the same general Multisegmented metallic nanowires can conveniently be
procedure can be applied irrespective of the materials to be prepared by sequentially changing the electrolytic solution
deposited (Figure 49). First, a thin Ag layer is deposited onto during the electrodeposition. Judicious control of the length of
one face of an AAO membrane. This Ag layer serves as the each segment allows one to obtain submicrometer barcodes,
working electrode in the deposition of desired materials. Next, a which can be used as platforms for multiplexed bio-
thin layer of sacrificial Ag (or Ni) is electrochemically deposited assays.251,344,354,355 The differential reflectivity of adjacent
into the pores. This process is recommended to avoid a so- metal segments and the selective self-assembly of appropriate
called “puddling effect” that typically causes nailhead shaping of molecules on specific metal segments enable the identification
one end of the deposited nanowire due to the geometric details of striping patterns by conventional optical microscopes. More
of the pore mouth.342 After that, the desired material is recently, multisegmented nanowires have been utilized for
electrochemically deposited. The resulting nanowires/AAO developing nanogap devices. Qin et al.356 developed a generic
composite sample then is dipped into HNO3 solution to approach to lithographically process 1D nanowires. The
remove the Ag working electrode layer and the sacrificial layer procedure, termed “on-wire lithography (OWL)”, involves
(Ag or Ni). The nanowires can be collected by dissolving the selective removal of one of the components comprising a
AAO template using an appropriate AAO etchant (typically, multisegmented nanowire to create gaps. Before gap creation
KOH or H3PO4). The choice of oxide etchant depends on the via the wet-chemical etching of targeted segment(s), one side of
material deposited; the etchant solution should not react with the multisegmented nanowires is subjected to the deposition of
the nanowire material. The diameter of the resulting nanowires a thin layer of insulting SiO2, which acts as a support for the
is determined by the pore size of the porous AAO template, nanogap device. In this way, the authors could create
while their length is proportional to the total amount of charge nanometer-sized gaps (5 to several hundred nm) on nanowires.
passed during the electrochemical deposition. Various metal Further, by employing dip-pen nanolithography, they deposited
nanowires (e.g., Au,264,343,344 Ag,344,345 Pt,343,346 Ni,343,347 nanoscopic amounts of conducting polymer within the created
Pb,348 Cu,348 Zn,349 Co,350−352 Sb353) have been synthesized nanogaps to investigate the transport properties of nanogaps.
in porous AAO templates. These single component 1D metallic More recently, Chen et al.357 demonstrated heterometallic
nanowires have been used as model systems for systematically nanogaps for molecular transport junctions (MTJs). Thiol-
investigating various research issues in chemistry and physics, terminated molecules were assembled into heterometallic
for example, the catalytic, magnetic, thermoelectric, and nanogaps (i.e., Pt/2-nm gap/Au) to observe their molecular
plasmonic properties of 1D nanostructures. Although single diode behavior. The on-wire lithography (OWL) technique was
component metallic nanostructures (e.g., nanowire or nano- further extended to develop a new encoding system by the
tube) are useful for studying structure−property relations, we same group. By taking advantage of the facile control of the
AQ dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
length of segments in the nanowire, dispersible 1D objects (Figure 52).367−373 In pulsed electrochemical deposition using
containing arrays of nanodisks were prepared and function- a two-component electrolytic solution, the cathodic potential is
alized with Raman active chromophores.358,359 This allowed
encoding of individual nanodisks both physically and
spectroscopically (Figure 50). As proof-of-concept, the authors
demonstrated multiplexed DNA detection at target concen-
trations as low as 100 fM.
Component materials in the multisegmented nanowires do
not need to be metals. They could be semiconductors or
conducting polymers. Park and co-workers.360,361 have found
that two-component nanorods consisting of metal/conducting
polymer layer can behave as mesoscopic amphiphiles. They
synthesized segmented Au/polypyrrol (Ppy) nanorods by
electrochemical deposition of Au into porous AAO template,
followed by electrochemical polymerization of pyrrol.360 The
length of each segment could be conveniently tuned by
controlling the deposition time (i.e., the total amount of Figure 52. TEM analysis of a freestanding Fe/Au barcode nanowire:
charge). Au/Ppy nanorods released from the template exhibited (a) elemental line scanning of Fe and Au composition along the
amphiphilic characteristics that originated from hydrophilic Au nanowire (Au, red; Fe, green), (b) elemental mapping of Au, and (c)
segments and hydrophobic Ppy blocks. Individual Au/Ppy elemental mapping of Fe. Reprinted with permission from ref 643.
nanorods self-assembled into microscale 2D sheets or 3D Copyright 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
bundles or tubes depending on the Au/Ppy segment length
ratio (Figure 51).
alternately pulsed between values above and below the
reduction potential of the less noble metal component.362
When the less negative potential is pulsed, more noble metal is
exclusively deposited. However, when depositing a less noble
metal by pulsing the more negative potential, the more noble
metal can be co-deposited. Therefore, the concentration of the
nobler metal ions should be held low enough as compared to
that of the less noble metal ions, so that the deposition of the
nobler metal ions during the pulsing of more negative potential
is limited by ion diffusion.342,362 Recently, Liu and co-
workers374 have demonstrated fabrication of tailor-made
inorganic nanopeapods (i.e., Co@CoAl2O4) nanowires by
pulsed electrochemical deposition of Co/Pt multilayers into
porous AAO template, followed by a solid-state reaction
between Co and Al2O3 at a high temperature.
Fabrication of multisegmented metal nanotubes has also
been demonstrated by Lee et al.375 Their method was based on
the preferential electrochemical deposition of metal along the
surface of pore walls decorated with metallic nanoparticles. The
authors immobilized Ag nanoparticles (AgNPs) on the pore
Figure 51. SEM images of “open” superstructures formed by wall surfaces of an AAO template by utilizing spontaneous
kinetically controlled, shape-directed assembly of Au/polypyrol reduction of Ag+ by Sn2+ as the following reaction:
(Ppy) nanorods: (a) a superstructure that has not fully closed, (b) a
fully closed superstructure, and (c) a physically cleaved area of the 2Ag +aq + Sn 2surface
+ 4+
→ 2Ag 0surface + Sn surface (70)
superstructure showing the individual rods that have been assembled
into the superstructure. Scale bars for (a,b) = 100 μm. Scale bar for (c) The process for AgNP immobilization is a simple variation of
= 50 μm. Reproduced with permission from ref 361. Copyright 2008 the well-established sensitization-pre-activation protocol ap-
Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. plied to AAO376,377 or track-etched polycarbonate tem-
plate338,378 prior to the electroless deposition of metals (see
As a more convenient approach, pulsed electrochemical section 9.2). Sn2+ was first chemisorbed on the pore wall
deposition can be used for the preparation of multisegmented surfaces by dipping the AAO membrane into an aqueous
nanowires with prescribed periodicity. Yahalom and Zadok362 mixture solution of 0.02 M SnCl2 and 0.01 M HCl for 2 min.
utilized pulsed electrochemical deposition technique to After thorough rinsing with water and drying, the resulting
fabricate Cu/Ni superlattice films by using a single electrolyte AAO template was immersed into 0.02 M AgNO3 solution.
containing Cu and Ni salts. Pulsed electrochemical deposition This cycle, usually repeated about six times, resulted in uniform
has been extended by other researchers to prepare multilayered deposition of AgNPs on the oxide surfaces. With the AgNP-
films of magnetic/nonmagnetic metal couple to investigate the immobilized AAO template, metallic nanotubes, embedded in
giant magnetoresistance (GMR) effect.363−366 The technique the AAO, were synthesized by electrochemical deposition. By
has also been implemented in track-etched polycarbonate periodically changing the electrolytic solution during electro-
membrane or porous AAO membrane to synthesize periodi- chemical deposition of the metal, the authors could synthesize
cally multisegmented metal nanowires with sharp interface mutisegmented Au/Ni nanotubes (Figure 53).
AR dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
Kohli et al.381 noted that the above electroless deposition

method applied to polycarbonate membranes does not work in
porous AAO templates because of insufficient binding sites for
the Sn2+ on the pore wall surfaces. The authors solved this
problem by modifying the surfaces of porous AAO with 2-
(succinic anhydride)propyl trimethoxysilane (SAPT), which
forms covalent Al−O−Si bonds with −OH functionalities on
the oxide surfaces. The anhydride in the SAPT molecule
hydroyzes to dicarboxylic acid, which chelates Sn2+ ions during
the sensitization process. As an alternative approach to increase
the density of oxygen groups on the oxide surface, Yu et al.394
incubated porous AAO membrane in 35% hydrogen peroxide
solution prior to Sn2+-sensitization. The rate of electroless Au
deposition was reported to increase with the pH of the plating
bath.381 Uniform Au nanotubes within pores of AAO templates
have been obtained by performing electroless deposition at the
pH < 10 and at temperature below 4 °C.381,394 At pH > 10 or at
a high temperature, either porous AAO dissolves and/or the
pores of the AAO template become closed due to the higher
rate of metal deposition relative to the rate of mass transfer of
Au(I) and formaldehyde down to the pores. Yu et al.394
reported that Au nanotubes formed by electroless deposition
are characterized by nanoclustered morphology, in which the
Figure 53. SEM images of multisegmented metal nanotubes with a size of the gold nanoclusters increases with the pH of the
stacking configuration of Au/Ni/Au/Ni/Au along the nanotube axis: plating bath. They showed that the size of the gold nanoclusters
(a) false-colored cross-sectional SEM image of as-prepared metal determines the catalytic properties of Au nanotubes embedded
nanotube-AAO composite. (b,c) SEM images of mutisegmented metal
in AAO membrane. Further, they showed that Au nanotubes/
nanotubes after removal of the AAO template. Adapted with
permission from ref 375. Copyright 2005 Wiley-VCH Verlag GmbH AAO composite membranes can be reused in the catalytic
& Co. KGaA, Weinheim. conversion of 4-nitrophenol into 4-aminophenol in the
presence of NaBH4 as a reductant.
9.2. Electroless Deposition (ELD) Activation of the porous AAO membranes can also be
accomplished by immobilizing PdNPs on the pore wall
Electroless deposition of metals into porous templates was
surfaces.395−397 Fabrications of arrays of Co,398 Ni,398
pioneered by Martin and co-workers.378−381 Most of the earlier
Cu,398,399 Pd,400 Pt,400 binary398 or ternary401 metal alloy
works were devoted to electroless deposition of gold within the
nanotubes, nanowires,402 and nanocones403 have been
pores of track-etched polycarbonate membranes. The typical
demonstrated by electroless deposition of metals into PdNP-
deposition process is composed of the following three general
immobilized porous AAO membranes.
steps:378,382,383
(1) Sensitization: This is accomplished by immersing the 9.3. Sol−Gel Deposition
porous polymeric template into an aqueous solution of SnCl2 Sol−gel processing has developed into a versatile protocol for
to deposit Sn2+ onto the surfaces of the membrane. the stoichiometric synthesis of diverse nanocrystalline materials.
(2) Activation: This is accomplished by dipping the Sn2+- In general, sol−gel chemistry involves the hydrolysis of
sensitized polymeric membrane into a AgNO3 solution, which precursor molecules under an acidic condition to prepare a
yields metallic AgNPs on the membrane surfaces through a suspension of colloidal particles (i.e., sol) and the subsequent
surface redox reaction (see reaction 70). condensation of the sol particles to obtain a gel. The resulting
(3) Electroless deposition: This entails immersing the gel is then calcined to obtain the desired material. Metal
activated polymeric membrane into a gold plating solution, in alkoxides in organic media or inorganic salts in aqueous media
which the surface-bound AgNPs act as catalyst for the can be used as precursors. Martin and co-workers pioneered the
reduction of Au+ to yield AuNPs on the membrane surface sol−gel porous AAO templating method for the synthesis of
through the following reaction. various semiconductor or insulator oxide nanostructures
Au+aq + Ag 0surface → Ag 0surface + Ag +aq (71)
(nanowires and nanotubes) including TiO2, ZnO, WO3,
V2O5, MnO2, Co3O4, and SiO2.404−406 Since then, many
The surface-bound AuNPs act as autocatalysts for the reduction investigators have employed the sol−gel deposition method to
of Au+ to metallic Au0 in the presence of a reducing agent (e.g., prepare a vast variety of oxide nanostructures to investigate, for
formaldehyde). Au deposition starts at the entire surface of example, photovoltaic (TiO2),407,408 gas sensing (SnO2,
membrane (i.e., pore walls and membrane faces). As a result, ZnO),409,410 ferromagnetic (CoFe2O4),411,412 ferroelectric
the surfaces of pore walls and the faces of the membrane can be (BiFeO3, SrBi2Ta2O9, PbZr0.52Ti0.48O3),413−415 superconduct-
coated with a thin Au layer, yielding Au nanotubes within the ing (YBa2Cu3O7-δ, Bi2Sr2CaCu2Oy),416,417 and luminescence
pores and continuous Au films on the faces of the membrane. (Y2O3:Eu, TiO2, ZnO:Dy) properties.418−420
The resulting gold nanotube/polymer composite membranes Typically, when depositing sol−gel into oxide nanopores, an
have been successfully used for diverse applications, for AAO is directly dipped into a solution containing sol particles
example, for selective ion-transport,379,382−387 (bio)molecule for a given period of time. After thermal treatment, either
separations,380,388,389 biosensing, and electroanalysis.390−393 nanowires or nanotubes of inorganic oxide are formed within
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the pores. In general, immersion of porous AAO template into the authors were able to synthesize very thin single-crystalline
a sol solution for long periods of time yields nanowires, while TiO2 nanowires (diameter ≈ 10 nm) by performing heat-
immersion for short periods of times yields nanotubes. The treatment and subsequently removing the AAO template.
formation of nanotubes indicates that the sol particles are As a surface modification protocol, the sol−gel template
adsorbed onto the pore wall surfaces due to electrostatic technique offers a large degree of freedom in nanotechnology
interaction between the negatively charged pore wall surfaces applications of porous AAO. Lee et al.425 demonstrated that
and the positively charged sol particles.404 Lakshmi et al.404 sol−gel-derived silica nanotubes/AAO composite can be used
reported that the gelation occurs at a faster rate within the as a synthetic bio-nanotube membrane for separating two
nanopores than in the bulk reservoir, due possibly to local enantiomers of a chiral drug, in which individual silica
increase in sol concentration at the pore wall surfaces. In their nanotubes act as nanometer-sized chromatography columns
SiO2 nanotube synthesis, Zhang et al.421 found that the in parallel. They deposited thin-walled (<3 nm) silica
viscosity of the sol solution is a key factor determining the nanotubes within porous AAO by adopting sol−gel template
morphology of the resulting nanotubes. Viscosity of sol synthesis approach. Subsequently, the inner wall surfaces of the
solution increases with aging time. They obtained nanowires silica nanotubes were functionalized with aldehyde terminated
from a porous AAO templated dipped for 1 min in a sol silane. This surface functionalization allowed the conjugation of
solution aged at room temperature for 2 days. From a solution an antibody that selectively binds to one enantiomer of a drug
aged for 30 days, they obtained SiO2 nanotubes connected with 4-[3-(4-fluorophenyl-2-hydroxyl-1-[1,2,4]triazol-1-yl-propyl]-
nanowires. They also found that the formation of the benzonitrile, which has two chiral centers and four stereo-
nanotubes depends strongly on the temperature of the sol isomers: RR, SS, SR, and RS. The silica nanotubes can be
solution. For a short dipping time less than 1 min, bamboo-like individually released from the porous AAO template to obtain
nanowires were prepared from a sol solution at 50 °C. On the silica nano test tubes.426−428 In another study, the inner and
other hand, perfect nanotubes with sharp walls were outer surfaces of silica nano test tubes were selectively
synthesized from a solution at a lower temperature (5 °C). derivatized with different functional groups using silane
As the temperature of the sol solution decreased, the inside wall chemistry.426 Silica nano test tubes with hydrophilic outer
of SiO2 nanotube became smoother. and hydrophobic inner surfaces were demonstrated to be ideal
Limmer et al.422 pointed out that filling of sol particles into for extracting lipophilic molecules from aqueous solution.426 In
oxide nanopores is mainly driven by the capillary force. Heat- addition, they can be capped with either polystyrene latex
treatment of the sol-coated AAO templates often results in 1D nanoparticles429 or gold nanoparticles427 to create nano-
porous nanostructures or hollow tubes due to insufficient capsules. Their facile surface functionalization, loadable large
packing of sol particles with the oxide nanopores. Limmer and hollow interior, low level of cytotoxicity, and ease of dispersion
co-workers422,423 developed an electrophoretic sol−gel process make the silica nano test tubes an effective drug/gene delivery
to resolve the problems associated with low particle packing system.428,430
density. In their approach, the electrophoretic motion of the Yamaguchi et al.431 demonstrated that a porous AAO
positively charged sol particles under an electric field is utilized. template can used to fabricate a silica−surfactant hybrid
The authors demonstrated successful syntheses of technolog- membrane containing nanochannels oriented in parallel with
ically important oxide nanowires (e.g., TiO2, BaTiO3, SiO2, respect to the pore axis of AAO. They used a precursor solution
SrNb2O6, Pb(Zr,Ti)O3; diameter = 70−200 nm) by electro- containing tetraethoxylsilane (TEOS) as the silica source and
phoretic deposition of sol particles into nanopores of track- cationic cetyltrimethylammonium bromide (CTAB) as a
etched polycarbonate membranes followed by heat-treat- structure guiding agent. By applying moderate aspiration, the
ments.422,423 authors were able to introduce precursor solution into the
Although the electrophoretic sol deposition process has pores of the AAO. Plastschek et al.432,433 demonstrated that the
distinct merit, it is rather difficult to apply the process to porous orientation of mesoporous silica structure in porous AAO can
templates with smaller pore diameters (<50 nm).422 The be systematically adjusted through combination of sol−gel
problem may arise due to the decreased diffusivity of sol process and evaporation-induced self-assembly. Systematic
particle in narrower pores or the size of the sol particles variations of the type and amount of structure guiding agent
(typically, 10−100 nm). To resolve this issue, Maio et al.424 and also the amount of added inorganic salts allowed the
employed a cathodically driven sol−gel process and prepared authors to investigate systematically the confinement effect of
single crystalline TiO2 nanowires. The authors employed a Ti the interfacial interaction on the orientation of silica nano-
precursor solution containing NO3− ions. The local increase in channels. Their experiments revealed that ionic CTAB
pH at the surface of electrode under a cathodic bias gives rise to produces a columnar hexagonal 2D structure parallel to the
the hydrolyzation of the Ti precursor through the following vertical nanochannels of the porous AAO membrane, whereas
reactions:424 nonionic surfactants, such as Pluronic P123 [poly(ethylene
NO−3 + 6H 2O + 8e− → NH3 + 9OH− (72) oxide)20-poly(propylene oxide)70-poly(ethylene oxide)20] and
Brij 56 [decaethylene glycol hexadecyl ether], prefer the
TiO2 + + 2OH− → TiO(OH)2 (sol) (73) formation of either a circular hexagonal 2D structure normal to
the nanopores of AAO or a structure with phase mixtures of
The resulting TiO(OH)2 sol particles are converted into a 3D circular and columnar orientations (Figure 54). Platschek et al.
network of titanium oxyhydroxide gel within the nanopores of found that the moisture content of the deposited sample and
AAO template via the following electrochemical reaction: the relative humidity during the drying process influence the
TiO(OH)2 (sol) − x H 2O → TiO1 + x (OH)2 − 2x (gel) microscopic separation.433
(74)
The cylindrical pore morphology of AAO, and the pore’s
As such, both the sol formation and the subsequent gelation dimensional tuneability, make porous AAO an ideal model
occur within the nanopores. By taking advantage of this fact, system for systematically investigating the confinement effect
AT dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
a rather complex evolution of mesochannels with the geometric

confinements. Figure 55 summarizes the evolution of the
confined mesostructures as a function of the channel diameter
of AAO template. When the AAO nanochannel diameter was in
the range 55−73 nm, the confined silica−surfactant composite
mesophase consisted of three coaxial layers: a straight inner
mesochannel and two outer concentric mesochannels with
diverse morphologies of stacked doughnuts, single helix (S-
helix), or double helix (D-helix). For the confinement
dimension of 49−54 nm, a coaxial double-layer helix
mesostructure was evolved; the inner core = S-helix and the
outer layer = S-helix or D-helix. On reducing the confinement
dimension down to 34−45 nm, the inner core became a
straight mesochannel (diameter = 13−16 nm), and the outer
layer consisted of stacked doughnuts, S-helix, or D-helix. For
further reduced confinement dimension of 31 nm, a single-
layered D-helix mesostructure was observed. For confinement
dimension below 30 nm, inverted peapod-like mesoporous
morphology, rather than helical mesostructures, was observed.
For the confinement dimension below 18 nm, a line of aligned
mesocages was formed. The authors pointed out that the
mesoporous silica frameworks in their composite mesophases
can be preserved even after the surfactant removal, which is
markedly different from that case of confined polymers.
9.4. Surface Modification
Coupling appropriate molecules to the pore wall surface of
AAO can greatly expand the application capability of porous
AAO for the synthesis of new functional nanomaterials, sensing,
recognition, and the controlled release of biologically relevant
Figure 54. Plane view TEM images of (a) the columnar oriented molecules. Surface functionalization with appropriate molecules
hexagonal mesostructure templated with CTAB, (b) the sample or particles provides an opportunity for tuning of the surface
templated with Brij at 60% humidity, and (c) the sample templated properties of porous AAO, such as hydrophilicity, surface
with P123 at 60% humidity. Reproduced with permission from ref 432. charge, reflectivity, membrane selectivity, antifouling resistance,
Copyright 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. etc. The surfaces of porous AAO can be functionalized with a
wide variety of molecules, such as n-alkanoic or fluorinated
on molecular organization. We et al.434 synthesized silica−P123 organic acid,435−437 organosilanes,438,439 and phosphonic
composite mesostructures within cylindrical nanochannels of acids.438,440 On the other hand, most studies on surface
AAO by employing a sol−gel method. It is well-known that this modifications of porous AAO are based on silanization
precursor forms hexagonal silica mesostructures (i.e., SBA-15), chemistry. Organosilane compounds can be covalently bound
in which the long axes of the mesochannels are aligned parallel on the surfaces porous AAO membranes, by taking advantage
to the surface of flat substrates. However, the authors observed of the rich hydroxide groups on the oxide surfaces. Organo-
Figure 55. Summary of the experimentally observed evolution of mesostructures confined within AAO nanochannels of varying diameters.
Reproduced with permission from ref 434. Copyright 2009 Macmillan Publishers Ltd.: Nature Materials.
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Figure 56. Schematic procedure for fabricating an AAO membrane with three different layers displaying distinct chemical functionalities. Adapted
with permission from ref 442. Copyright 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
silanes on AAO surfaces can act as linkers to immobilize explosive molecule, 2,4-dinitrotoluene, the AuNP-decorated
nanoparticles, polymers, proteins, DNA, and other molecules AAOs with 3D nanochannel arrays exhibited Raman enhance-
for additional functionalities. Among a variety of organosilane ment with a factor of about 105, as compared to that observed
compounds, aminosilanes (e.g., 3-aminoproyl trimethoxysilane on a AuNP monolayer with identical surface densities of
(APTMS) or 3-aminopropyl triethosysilane (APTES)) have AuNPs. The authors suggested that the AAO membrane itself
most frequently been employed as coupling agents. could contribute extra enhancement of Raman signals, not only
Losic and co-workers441 have recently reported a new providing additional sites for molecule adsorption, but also
approach for controlling the surface architecture of porous guiding the light by the vertically aligned nanopores. A similar
AAO membranes, which generates layered, silane-based surface line of experimental results was also reported for AgNP-
chemistries and yields distinctly different functionalities on the decorated AAOs.449,450
pore openings and the internal pore surface. The method was Rubinstein et al.446 prepared nanoparticle-decorated nano-
based on the remarkable stability of the silanized surface of tubes (NPNTs) by passing a citrate-stabilized AuNP solution
AAO during anodization of aluminum. After a short-term first through the pores of the AAO membrane, the surface of which
anodization of aluminum and removal of most of the resulting was modified with APTMS (or APTES). The formation of Au
porous oxide, the surface of the remaining thin oxide layer was NPNTs was assumed to involve the aggregation of surface-
derivatized with ATPES. The resulting silanized sample was confined AuNPs accompanied by spontaneous room-temper-
subsequently reanodized for a longer period of time. The ature coalescence upon drying. With the same approach,
surfaces of the pore wall formed by the second-step anodization multiwalled bimetallic Au/Pd NPNTs were also prepared.451 In
were functionalized with hydrophobic pentafluorophenyldime- another study, Wang et al.398 utilized the terminal amine groups
thylchlorosilane (PFPES) with distinctly different properties of surface-attached APTES to complex with Sn2+-sensitizer in
from the APTES present in the pore opening. By extending the electroless depositions of Co, Ni, and Cu nanotubes within
work, they have also demonstrated that different functionalities pores of AAO template. The surface-bound Sn2+ reduced Pd2+
and wettabilities can be imparted to the pore channels of AAO. into metallic PdNPs, which acted as catalyst during the
Multilayered surface modifications of porous AAOs were electroless deposition of metals. Recently, Tanvir et al.452
achieved by repeating anodization and subsequent silanization immobilized covalently recombinant human cytochrome
of the pore wall oxide with different silane molecules, such as (CYP2E1) and glucose-6-phosphate dehydrogenase (G6PD)
APTES, PFPTES, and N-triethoxysilylpropyl-O-poly(ethylene on the pore wall of APTES-functionalized AAO membranes
oxide) urethane (PEGS) (Figure 56).442 The thickness of through N-succinimidyl-3-maleimidoproprionate and glutaral-
individual functional layers could be conveniently varied by dehyde cross-linker, respectively. The authors showed that the
controlling the anodization time. Deliberate combination of immobilized enzymes can retain 100% of the activity of free
silane molecules with different chemical properties allowed enzyme. A miniaturized heterogeneous membrane reactor was
selective membrane transports of small molecular compounds. realized by stacking two independently modified membranes
Decoration of inorganic nanoparticles on the pore wall and placing them in a fluidic device, in which the first
surface of AAO often imparts new properties to porous AAO. membrane regenerates the cofactor NADPH from NADP+ and
This decoration can be facilitated by surface modification of the glucose-6-phosphate and the second one utilizes it for CYP2E1-
pore wall surface with an organic monolayer or polymer,443−447 based catalysis. Likewise, a cell adhesion peptide has also been
but can also be achieved directly on the AAO.375,448,449 Ko and grafted on APTMS-derivatized porous AAOs to improve
Tsukruk443 immobilized AuNPs on pore walls modified with osteoblast adhesion.453 Swan et al.453 reacted the APTMS-
poly(diallydimethylammonium chloride) (PDDA) polyelectro- functionalized AAO membranes with N-succinimidyl-3-mal-
lyte by passing cetyltrimethylammonium bromide (CTAB)- eimidopropionate and subsequently with a cellular adhesion
stabilized AuNP solution through the AAO membrane. On an peptide, arginine-glycine-aspartic acid-cysteine (RGDC).
AV dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
Figure 57. (Left) Derivatization of PHEMA with NTA-Ni2+ prior to protein adsorption. (Right) Binding of his-tagged protein to an NTA-Ni2+
derivatized PHEMA brush inside pores of AAO. Adapted with permission from ref 456. Copyright 2007 The American Chemical Society.
Figure 58. Schematic diagram showing (a) the formation of thin polymer films using layer-by-layer (LbL) deposition of polyelectrolytes, (b) a
nanofiltration membrane prepared by the deposition of a multilayer polyelectrolyte film on AAO, (c) a membrane for protein purification created by
growing polymer brushes within pores of AAO, and (d) a catalytic membrane prepared by LbL deposition of polyelectrolytes and charged metal
nanoparticles. Adapted with permission from ref 462. Copyright 2008 The American Chemical Society.
Polymer brushes can also be grafted on the pore wall surfaces counterparts.143 Polymers grafted on AAOs can be also
of porous AAOs. Polymer-grafted porous AAOs exhibit an functionalized with biologically important molecules, such as
improved binding capacity, stability, selectivity, biocompati- proteins or DNAs. Recently, Li et al.454 prepared thermo-
bility, and lubricating characteristics as compared to bare responsive gating membranes with tuneable length and density
AW dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
of poly(N-isopropylacrylamide) (PNIPAM). The authors by activating with GPTMS. The pH-valve effect was observed
reacted an APTMS-functionalized AAO membrane with the at pH between 3 and 5. Electrochemical impedance spectros-
initiator 2-bromoisobutyryl bromide (BBIB), and then the copy (EIS) showed that the membrane resistance increased
resulting membrane with −Br groups was reacted with N- from 4.3 × 105 Ω cm2 at pH 2 to 1.3 × 106 Ω cm2 at pH 6.
isopropylacrylamide (NIPAM) monomers during atom-transfer The layer-by-layer (LbL) deposition method, which involves
radical polymerization (ATRP) to yield PNIPAM-grafted AAO the alternate adsorption of differently charged polyelectrolytes,
membrane (PNIPAM-g-AAO). The density of PNIPAM can be applied to the substrate surfaces that allow the
grafted on the pore wall surfaces could be controlled by adsorption of an initial polymer layer (Figure 58a).462−466
changing the number density of −Br groups (i.e., ATRP The resulting multilayer films can be further functionalized with
initiator). The themo-responsive characteristics of the nanoparticles or biomolecules. The most used polyelectrolytes
PNIPAM-g-AAO membranes were investigated by tracking are commercially available ones, such as poly(ethylenimine)
the diffusional permeation of vitamin B12 at temperatures (PEI), poly(allylamine hydrochloride) (PAH), poly-
below and above the lower critical solution temperature (diallydimethylammonium chloride) (PDADMAC), poly-
(LCST). The results indicated that thermo-responsive (styrenesulfonate) (PSS), poly(vinylsulfate) (PVS), and poly-
characteristics are heavily affected by both the length and the (acrylic acid) (PAA). LbL deposition of polyelectrolyte
density of grafted PNIPAM chains in the pores of AAO, and multilayer films on the surfaces of porous AAO membranes
the effect of the length of grafted PNIPAM chains is more was first demonstrated by the Bruening group (Figure 58b−
significant than that of the density. Purifications of proteins d).467 LbL deposition of PAH and Cu2+-complexed PAA on the
based on reusable metal affinity membranes have been surfaces of AAO membranes and subsequent controlled
demonstrated by the Bruening group. The use of ATRP to removal of Cu2+ and deprotonation allowed control of the
grow poly(2-hydroxyethyl methacrylate) (PHEMA) brushes in fixed charge density within PAA/PAH multilayer films (Figure
the pores of AAO, followed by functionalization of the PHEMA 58b). The resulting Cu2+-templated PAA/PAH-AAO mem-
with nitrilotriacetate-M 2+ (NTA-M2+; M = Cu or Ni) branes exhibited a 4-fold increase in Cl−/SO2− 4 transport
complexes, yielded AAO membranes that adsorbed proteins selectivity in comparison to Cu2+-free PAA/PAH-AAO
via coordination of M2+ to his-tagged proteins (Figures 57, membranes deposited under similar condition.467 Cross-linking
58c).455,456 In another study by the same group,457 two types of of Cu2+-templated PAA/PAH-AAO membranes further in-
ultrathin (∼50 nm) polymer brushes, linear PHEMA and cross- creased Cl−/SO2− 4 selectivity as high as 610. It was suggested
linked poly(ethylene glycol dimethacrylate) (PEGDMA), on that this selectivity might be due to both Donnan exclusion and
the pore wall surfaces of AAOs were synthesized using the diffusivity differences among ions. Size-selective transport of
ATRP method. Gas permeation studies showed that the neutral solute through PSS/PAH has also been reported by the
PEGDMA-AAO membrane had a CO2/CH4 selectivity of ∼20 same group.468 The number of bilayers combined with different
and an O2/N2 selectivity of ∼2, whereas uncross-linked compositions of multilayered films turned out to significantly
PHEMA-AAO membrane showed very low selectivity. influence the rejection, flux, and selectivity of charged solutes
However, the CO2/CH4 selectivity of PHEMA improved to through the membranes.468−470 In addition, deposition
∼8 after esterification of −OH groups of PHEMA with conditions such as pH, ionic strength of the polyelectrolyte
pentadecafluorooctanoyl chloride. Further derivatization of solutions, and the charge of the outermost polyelectrolyte layer
PHEMA-grafted AAO membranes with octyl, hexadecyl, or were also found to influence the molecular separation of
pentadecafluorooctyl side chains made the membranes hydro- cations.470 Polyelectrolyte films composed of PSS/PAH or
phobic, allowing selective removal of volatile organic PSS/PDADMAC+PSS/PAH films were reported to be effective
compounds (VOCs) from water via pervaporation.458 In in the selective removal of Mg2+ from aqueous solutions
another study by Bruening’s group,459 poly(ethylene glycol) containing NaCl and MgCl2 salts (i.e., water softening), while
(PEG)-grafted AAO (PEG-g-AAO) membranes were prepared pure PSS/PDADMAC films and commercial NF270 mem-
through ATRP of poly(ethylene glycol methyl ether meth- branes showed only relatively low rejections of Mg2+.470 For
acrylate) with different lengths of PEG chain from initiator- PAH-terminated multilayer films, Mg2+ rejection and Na+/Mg2+
modified porous AAO. The resulting PEG-g-AAO membranes selectivity increased with the increasing charge near the surface
contained a mixture of short and long PEG side chains, in of the polyelectrolyte multilayer films, by increasing the ionic
which the shorter PEG chain (8−9 ethylene oxide units) strength of the PAH deposition solution. LbL film-based
prevented crystallization, while the longer side chains (23−24 catalytic AAO membranes were also demonstrated by
ethylene oxide units) allowed the membranes to maintain a Bruening’s group.444 By utilizing the charge on the LbL films,
CO2/H2 selectivity of 12 at room temperature.459 Shi et al.460 citrate-stabilized AuNPs were immobilized within the pores of
prepared metal affinity membranes with uniform diameter and AAO. Au-immobilized LbL films within the pores of AAO
distribution of pores for protein separation and purification. membranes exhibited a similar rate constant for Au-catalyzed 4-
Chitosan(CS)-AAO membranes were prepared by activating nitrophenol reduction in solution and in membranes (Figure
the hydroxylated AAO with 3-glycidoxypropyl trimethoxysilane 58d). Covalent immobilization of antibodies on LbL films (i.e.,
(GPTMS), followed by CS grafting.460 Cu2+-attached affinity [PAA/PAH]3PAH) in the pores of AAO membranes has also
membranes were then obtained by immobilizing Cu2+ on the been realized via carbodiimide coupling between −COOH
CS-AAO, and were utilized for the separation and purification groups of PAA amine groups of antibodies.471 Detection limits
of hemoglobin from red cell lysate. Song et al.461 have reported in the analysis of Cy5-labeled IgG were reported to be 0.02 ng
preparation of pH-responsive poly(acrylic acid)-grafted porous mL−1 because of the high surface area of the porous AAO.471 In
AAO membranes. Silica-AAO composite membrane was first addition, resistance against nonspecific protein adsorption for
prepared by depositing silica onto the AAO membrane through these LbL film-AAO composites has also been reported.
the sol−gel method. The pH-responsive poly(arcrylic acid) Combination of the LbL technique and the AAO templating
(PAA) was grafted onto the silica-AAO composite membranes approach has been demonstrated its versatility in fabricating
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Figure 59. (a) Schematic illustration of a lipid bilayer formed by 1,2-diphytanoyl-sn-glycero-3-phosphocholin (DPhPC) onto a self-assembled 1,2-
diphytano-dipalmitoyl-sn-glycero-3-phosphothioethanol (DPPTE) monolayer chemisorbed on a gold-coated surface of a porous AAO substrate. (b)
Impedance analysis of a lipid bilayer bathed in 0.1 M Na2SO4 recorded in a frequency range of ω = 10−1−106 Hz before (■) and after (○)
gramicidin addition. The membrane resistance was dropped by >3 × 106 Ω from Rm = 8.73 × 106 Ω to Rm = 5.45 × 106 Ω. The solid line is the result
of a fitting routine using the equivalent circuit shown in inset. Adapted with permission from ref 496. Copyright 2004 The Biophysical Society.
Figure 60. Separation of attoliter-sized compartments employing pore spanning lipid bilayers. (A) composite z-stack image (total z-distance: 15 μm)
of pore-spanning lipid bilayer preventing avidin entrance into the underlying pores (black area). Main image: Lipid membrane is located at the
interface between the AAO and the bulk solution, showing both red fluorescence from the membrane and green avidin fluorescence in the overlayer.
The total image size is 67 μm × 67 μm. Top and right side images are line profiles along the z-direction, manifesting that the membrane prevents the
fluorescent labeled proteins from entering the pores. (B) A z-stack image of the membrane encapsulating pyranine dye molecules. The image size is
34 μm × 34 μm. Adapted with permission from ref 500. Copyright 2011 The American Chemical Society.
composite tubular nanostructures with various functional exhibit long-term stability. However, the close proximity
properties. Non-electrostatic interactions, such as hydrogen or (typically 0.2−2 nm) of a lipid bilayer to the surface of solid
covalent bonding and hybridization, have been utilized to support limits lateral lipid mobility, insertions of large
assemble quantum dots (QDs), nanoparticles, polymers, and transmembrane proteins to the lipid bilayer, or the generation
biologically relevant molecules or materials into functional of electrochemical gradient across lipid bilayer membranes,
nanotubes.445,462,472−481 which is required for selective transport of specific ions, for
Lipid bilayers are novel mimics of biological cell instance, in ion pumps and ligand- or voltage-gated ion
membranes.143 Free-standing bilayer lipid membranes recon- channels.486 Several approaches to decouple the lipid bilayer
stituted with ion-channel proteins provide an excellent system membrane from its underlying support have been developed to
not only for drug screening,482,483 but also for designing highly increase the lateral mobility. These include utilization of lipids
sensitive biosensors.484,485 Conventional solid supported with long hydrophilic spacers,487 water or polymer cushions
membranes (SSMs) methods utilize gold-thiol, silanization of between lipid membrane and solid support,488−491 and surface
OH-groups, and electrostatic interactions to immobilize lipid patterns with different thiol-components.492 On the other hand,
bilayers on solid supports.486 The immobilized lipid bilayers free-standing bilayer lipid membranes (also known as black
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lipid membranes, BLMs) have been formed across micrometer- template into a solution containing the desired monomers and
sized apertures in an attempt to eliminate the steric congestion the polymerization initiator or the electropolymerization within
in SSMs.485 Yet the fragility of the bilayer lipid membranes on the cylindrical nanopores.338,406,506−509 Electropolymerization
micrometer-sized apertures often prevents their practical has been utilized to synthesize conducting polymer nanotubes
applications. The mechanical stability of BLMs can be increased within the pores of AAO or track-etched polycarbonate
by reducing the aperture size.493,494 However, the increased membranes. Electrically insulating polymer nanotubes have
stability comes at the expense of reduced effective membrane also been prepared chemically. For example, polyacrylonitril
area to which proteins can be incorporated. (PAN) nanotubes with controlled inner diameters were
Pioneering works by Steinem et al.486 have led to the synthesized by dipping a porous template into a solution
development of methods for suspending lipid bilayers on the containing acrylonitrile and a polymerization reagent, in which
pores of porous AAO, bridging the technical gap between polymerization time determined the inner diameter of
conventional SSMs and BLMs. First, the authors selectively nanotubes.510
functionalized the top surface of porous AAO (Dp = 60 ± 10 With an alternative approach, Steinhart et al.511 developed an
nm) by chemisorbing 3-mercaptopropionic acid (MPA) onto arguably simple, yet highly versatile technique for the
10-nm-thick Au layer that was pre-deposited onto the AAO. fabrication of functional polymer nanotubes. The method is
Next, the MPA-modified surface was negatively charged by based on the spontaneous spreading (or wetting) of a polymer
treating with 10 mM tris(hydroxymethyl)aminomethane) melt or its solution on a surface with high surface energy to
solution (pH 8.0). Finally, a pore-spanning lipid bilayer was form the so-called “precursor film”.512−514 Surface wetting
obtained by adsorbing positively charged vesicles of N,N- behavior of a droplet of a liquid is described by the spreading
dimethyl-N,N-dioctadecylammonium bromide (DODAB) onto parameter S:513
the negatively charged MPA monolayer. Pores of AAO spanned S = γsg − γsl − γlg (75)
by bilayer lipid membranes are tunable in a nanometer range.
Moreover, because the pore channels of AAO are separated by where γsg, γsl, and γlg, respectively, are the solid−gas, solid−
a semipermeable lipid membrane from the outer solution, they liquid, and liquid−gas interfacial tensions. If S is negative, a
can serve as nanocontainers for bio-reaction and for establish- liquid drop on the substrate adopts an equilibrium shape
ment of electrochemical gradients.495 Extending their previous corresponding to a finite contact angle θe defined by Young’s
works, Steinem et al.496−499 showed that pore-spanning lipid condition cos θe = (γsl − γsg)/γlg. If S is positive, spontaneous
bilayers on porous AAO substrates are electrically insulating, spreading of the liquid occurs because the adhesion forces
and also demonstrated that the ion-channel proteins recon- between the liquid and the solid substrate dominate the
stituted in bilayer membranes are fully functional (Figure 59). cohesive forces within the wetting liquid, and the equilibrium
More recently, the same group of authors employed pore- situation corresponds to complete coverage of the substrate by
spanning lipid bilayers formed by spreading a giant unilamellar the precursor film with a thickness ranging from several
vesicle (GUV) on porous AAO substrates to create attoliter- angstroms to tens of nanometers (i.e., θe = 0).513,515
sized compartments, which were used not only for entrapment Accordingly, direct contact of porous inorganic templates
but also for exclusion of materials. By taking advantage of the (i.e., high-surface-energy materials) with polymer melts or
optically transparent nature of porous AAO substrates, solutions (low-surface-energy materials) results in the immedi-
fluorescent molecules inside the compartments (i.e., AAO ate wetting of pore wall surfaces with thin precursor film
pores) as well as the lipid membranes on top of the pores could (Figure 61a). Steinhart et al.515 suggested that pore wall wetting
be visualized by using confocal laser scanning fluorescence is kinetically stable (but thermodynamically unstable), when the
microscopy (Figure 60).500 This technique will become strong adhesive forces between the liquid and solid are
powerful in biosensing applications, if it is combined with the neutralized upon complete surface wetting, due to the finite
recently developed label-free nanoporous optical waveguide surface area of an individual pore of the template. To attain a
sensor by Hotta et al., in which changes in reflection spectra of thermodynamically stable state (i.e., complete pore filling), the
the AAO/Al multilayer films were measured in the cohesive force should dominate the viscous forces of the
Kretschmann configuration, similarly to the conventional wetting liquid. Thus, pore wall wetting and complete filling
surface plasmon resonance (SPR) sensor.501 occur on different time scales; the latter, if it would happen at
Smirmov and Poulektov502 demonstrated that phospholipid all, will require several months or even several years of
bilayers can self-assemble to form nanotubes within the pores time.515,516 Therefore, polymer nanotubes can be obtained by
of AAO membrane by exposing one side of membrane to an solidifying the wetting liquid before complete pore filling
aqueous dispersion of phospholipid. The formation of lipid (Figure 61b−d). According to Steinhart et al.516 complete pore
nanotubes was been confirmed by spin-labeling electron filling occurs when the pore diameter of the porous template is
paramagnetic resonance (EPR),502 solid-state NMR spectros- smaller than the thickness of wetting layer (10−30 nm). The
copy,503 and fluorescence microscopy.504 In another study, wetting layer thickness may depend on the nature of polymer
Demé and Marchal505 prepared polymer-cushioned lipid and the surface state of wetting solid. It was reported that
bilayers within the pores of AAO. Their preparation approach injection of polystyrene (PS) melt into the pores of AAO (Dp =
consisted of direct fusion of lipid vesicles into the poly(ethylene 40 nm) results in arrays of PS nanowires, rather than
glycol) (PEG)-derivatized pores of AAO. nanotubes.517
On the basis of the experimental observations of
9.5. Template Wetting
spontaneous surface spreading of highly viscous melts of
Pores of AAO template can be utilized as nanoreactors for the polymers with ultrahigh molecular weights (typically, 106 and
synthesis of a variety of nanotubular materials. The template- 107 g mol−1), Steinhart et al.516 suggested that wetting of
based chemical syntheses of polymer nanotubes, pioneered by polymer melt or solution would occur through surface
C. R. Martin, typically involve either the immersion of a porous diffusion. Therefore, individual polymer chains should align
AZ dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
mixture solutions containing Pd(OAc)2 and poly(D,L-lactide)

(PDLLA) at 350 °C, in which the PDLLA acts as a reducing
agent for PdII at 160 °C and pyrolyzes at a higher 350 °C.521
The method was extended to prepare Pt nanotubes from
Pt(acac)2/PDLL composite nanotubes.522
9.6. Mask Techniques
Two-dimensional (2D) periodic arrays of nanostructures (e.g.,
semiconductors, metal nanoparticles, or complex oxides arrays)
have attracted tremendous research attention because of their
many unique properties and promising applications in
electronic/optoelectronics, bio-sensing, and high-density data
storage media. In 1996, Masuda and Satoh6 reported for the
first time the fabrication of arrays of gold nanodots on silicon
substrate by using ultrathin AAO as a stencil mask for
depositing gold. Since then, thin AAO-based surface patterning
has been popularized. The interested reader is referred to
review articles on surface nanopatterning using ultrathin AAO
masks given in refs 523 and 524. AAO-based surface patterning
methods are highly attractive in terms of throughput,
accessibility, cost, and compatibility with high-temperature
nanofabrication processes, in comparison to other surface
Figure 61. (a) Wetting of porous templates with polymer melts or nanopatterning techniques (for example, electron-beam direct
solutions: (i) The fluid comes into contact with the template. (ii) writing (EBDW), focused ion beam (FIB) milling, nano-
Within a second, the pore walls are covered with a thin film of the imprinting lithography (NIL), and scanning probe microscope
liquid. By freezing this stage, nanotubes are preserved. (iii) A complete (SPM)-based writing).
filling of the pore space was not observed. (b−e) SEM images of
Ultrathin AAO membranes can be transferred onto desired
polymer nanotubes obtained by melt-wetting: (b) polystyrene (PS)
nanotubes embedded in porous AAO, (c) PS nanotubes after removal substrates by supporting AAO membranes with appropriate
of AAO template, (d) array of polytetrafluoroethylene (PTFE) polymers (typically, poly(methyl methacrylate) (PMMA) or
nanobues, (e) poly(methyl methacrylate) (PMMA) nanotubes. Panel PS).6,523 In this method, a thin polymer layer is coated on one
(a) was reproduced with permission from ref 515. Copyright 2003, face of the ultrathin porous AAO film. Afterward, the aluminum
Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Panels (b−e) substrate and the barrier layer at the bottom of the pores are
reprinted with permission from ref 511. Copyright 2002 AAAS. removed. Next, the resulting AAO/polymer composite film is
transferred onto a substrate of choice. Finally, the polymer is
on the wetting surface. The cylindrical geometry of pores in removed by immersing the sample into an appropriate solvent
AAO imposes a spatial confinement with respect to the or by performing oxygen plasma treatment. However, this
movement of a polymer chain, in which the length of the pore method often suffers from the difficulty in transferring a large-
channel can be regarded as infinite, while the circumference and scale ultrathin AAO membrane onto a substrate without
thickness of the wetting polymer are finite with a curvature. introducing structural damages caused by folding, cracking, or
Poly(vinylidene difluoride) (PVDF) nanotubes prepared by ripping of the ultrathin AAO. Recently, Meng et al.525
melt-wetting of porous AAO (Dp = 400 nm) exhibited a demonstrated the successful transfer of wafer-scale ultrathin
curvature-directed crystallization to form α-PVDF phase, in AAO membranes (thickness = 200 nm) onto hydrophilized
which the crystallographic b-axis of α-PVDF is parallel to the substrates. The method involved selective etching of the
long axis of the nanotubes, the only direction to minimize underlying aluminum of a two-step anodized AAO film to leave
curvature constriction.518 The effects of geometric confinement a rigid aluminum frame surrounding the AAO film, followed by
and the pore wall on the mesophase formation of liquid transfer of the resulting aluminum-frame-supported AAO film
crystalline materials have also been reported.519,520 onto a desired substrate (Figure 62). The aluminum frame
Template wetting is versatile in terms of the facile variation stabilized the ultrathin AAO film during transfer. The
of tube wall materials. Almost all polymer solutions with a low hydrophilic surface of the substrate enabled a conformal
surface energy can be used to synthesize functional or contact between the ultrathin AAO film and substrate via
composite nanotubes. Preparations of polymer nanotubes dropping water on the substrate. After removal of the
with high technical importance (e.g., polyether ether ketone surrounding aluminum frame, the barrier oxide layer could be
(PEEK) or polytetrafluoroethylene (PTFE)), which are very removed by conducting argon milling to obtain a through-hole
difficult or practically impossible to process by conventional AAO membrane.
methods (e.g., extrusion or injection molding of polymer), have A variety of materials have been fabricated into ordered
been demonstrated by wetting of polymer melt impregnation arrays of nanostructures on substrates of choice, including
into porous templates.516 Multicomponent composite nano- arrays of semiconductor,526−535 metal,536−539 and oxide
tubes have also been utilized to prepare inorganic nanotubes. In nanodots540−546 or arrays of nanoholes,547−562 nanorings,563
this case, the polymers are mixed with inorganic precursors and nanopillars,548 and nanowires.525,564 Figure 63a−d schemati-
act as a carrier in the wetting process. Chemical transformation cally shows the general procedures for the fabrication of 2D
of the inorganic precursors within the composite nanotube extended arrays of (a) nanoholes, (b) nanodots, (c) nanopillars,
walls yields inorganic nanotubes. For example, Pd nanotubes and (d) nanowires by using ultrathin AAO membranes as
were prepared by the wetting of porous AAO templates with masks. Ordered arrays of nanoholes have been fabricated on
BA dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
also been used either as etching masks in dry etching processes

to generate ordered arrays of nanopillars (Figure 63c)548,553 or
as catalysts in the chemical vapor deposition (CVD) growth of
arrays of carbon nanotubes (CNTs),565 the MBE growth of
GaAs nanowires,566 and the vapor−liquid−solid (VLS) growth
of Si,564 MgO,525 and ZnO567 nanowires (Figure 63d).
Thick porous AAO membranes have been utilized as
replication masters for preparing metallic stencil masks. Lee
et al.568 demonstrated that Au nanotube membranes replicated
from porous AAO can be utilized as deposition masks for
fabricating 2D periodic arrays of catalyst nanodots for site-
specific VLS growth of semiconductor nanowires (see Figure
64)569,570 or ordered arrays of ferroelectric nanostruc-
tures.568,571,572 Their fabrication of Au nanotube membranes
involved the sputter deposition of thin Au film on the pore wall
Figure 62. (a) Schematic procedure for the fabrication of ultrathin surfaces of top part of AAO membrane, as well as on the top
AAO membrane on a substrate. Photographs of 200-nm-thick AAO membrane surface, followed by electrochemical deposition of
membrane (b) supported by Al frame and (c) transferred onto a 3-in.
silicon wafer. Reproduced with permission from ref 525. Copyright
Au, to further thicken the metal layer. Subsequent removal of
2012 The Royal Society of Chemistry. the AAO membrane by floating the sample on 30 wt % H3PO4
solution resulted in a free-standing Au nanotube membrane.
Finally, Au nanotube membrane was transferred onto desired
various substrates by conventional dry processes, such as substrate. The replicated Au nanotube membranes exhibited a
plasma etching, reactive ion etching (RIE), and ion milling high degree of flexibility, allowing conformal contact even with
(Figure 63a). Because of high nanohole regularity and density, curved surfaces. In the process, the inner diameter of the Au
the resulting nanostructures exhibited many interesting proper- nanotubes can be easily tuned by controlling the electro-
ties that can be exploited in the development of effective deposition time. Therefore, nanodots with sizes smaller than
antireflection structures,555,556 high performance electrodes or the pore diameter of the starting AAO could be fabricated.568
capacitors,559,560 waveguides and photonic crystals,561 and With a similar approach, replications of ultrathin (thickness ≈
optical or lasing devices.549,562 On the other hand, arrays of 20 nm) metal meshes with arrays of ordered nanoholes have
nanodots can simply be obtained by depositing a desired also been reported. The replicated metal meshes have been
material through an ultrathin AAO membrane (Figure 63b), in utilized not only as stencil masks for the patterning of polymer
which a 2D array pattern, and size and interdistance of the substrates,573 but also as catalysts for the metal-assisted
nanodots are defined by those of the ultrathin AAO mask. Most chemical etching of silicon wafers to prepare arrays of silicon
physical vapor deposition (PVD) methods can be employed to nanowires with controlled size, surface morphology, and
create surface nanostructures, including e-beam evapora- crystallographic orientations (Figure 65).573−578
tion,6,533,534,539,548 thermal evaporation,527,528,540 sputter depo-
9.7. Chemical Vapor Deposition (CVD)
sition,535 pulsed laser deposition (PLD),541−546 and molecular-
beam epitaxy (MBE).526,530−532 The generated nanodot arrays A major challenge facing the chemical vapor deposition (CVD)
have been used as model systems for investigating the of materials into the pores of AAO involves achieving a uniform
structure−property relations of materials (e.g., magnetism, deposition of materials on the entire surface of the pore walls. A
plasmonics, photoluminescence, cathode luminescence, ferroe- fast rate of deposition may cause blockage of pores before the
lectricity) at nanometer-length scales. Arrays of nanodots have precursor chemical vapor traverses pores of high aspect
Figure 63. Schematic procedure for the fabrication of 2D extended arrays of (a) nanoholes, (b) nanodots, (c) nanopillars, and (d) nanowires by
using ultrathin AAO membranes as mask.
BB dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

emitters,585 electrodes for supercapacitors,588 and platforms for

intracellular delivery.589
Porous AAO has also been utilized as a structure-guiding
template in CVD growth of nanowires. It has been well
established for the VLS growth of SiNWs that the nanowires
grow preferentially along the ⟨111⟩, ⟨112⟩, or ⟨110⟩ directions
depending on the diameter.590,591 At the same time, vertically
aligned [100] SiNWs on Si(100) substrate are highly desired
for most practical applications in current complementary-metal-
oxide-semiconductor (CMOS) technology. Moreover, tight
control over the diameter and spacing of SiNWs in conven-
tional VLS growth process is difficult to achieve without
employing electron beam lithography to define the size and
location of the catalyst nanoparticles. Shimizu et al.592
demonstrated homoepitaxial growth of SiNWs on Si(100)
substrate by utilizing porous AAO as an orientation guiding
template. The method entailed the combination of electroless
deposition of Au catalyst into AAO nanopores and VLS growth
of Si (Figure 67). This approach has recently been extended by
Gorisse et al.593 to prepare extended arrays of vertically aligned
[100] SiNWs with tightly controlled diameters and separations.
Fabrications of other semiconductor nanostructures by CVD
techniques have also been reported. Cheng et al.594 obtained
single crystalline GaN NWs in porous AAO templates by
reacting Ga2O3 vapor with NH3 gas at 1000 °C. The authors
suggested that the defects in the pore walls act as GaN
nucleation centers under a saturated reaction atmosphere, and
the multiplication of screw dislocations is responsible for the
unidirectional growth and formation of GaN NWs. Later, this
method was modified by Zhang et al.,595 who employed indium
nanoparticles electrodeposited in AAO pores as catalyst, to
prepare ordered arrays of GaN nanowires. VLS growth of
hexagonal wurtzite GaN nanowires with very miscible droplets
of In−Ga−N was also suggested. Jung et al.596 reported
Figure 64. (a) SEM image of Au catalyst nanodots deposited using an fabrication of GaN nanotubes by metallorganic chemical vapor
Au nanotube membrane as a shadow mask. (b) Top-view SEM image deposition (MOCVD) using trimethylgallium (Ga(CH3)3) and
of VLS-grown ZnO nanorod arrays using Au catalyst nanodots shown ammonia (NH3) as precursors. Because of the random
in (a). Reproduced with permission from ref 569. Copyright 2006 nucleation of GaN nanoparticles on the surfaces of the inner
Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. pore wall of AAO, the fabricated GaN nanotubes consisted of
GaN nanoparticles with sizes of 15−30 nm. In another study, Li
et al.597 reported the controlled growth of Ge nanowires or
ratio.579,580 The uniform deposition of carbon was first reported nanotubes inside a porous AAO template by low-temperature
by Kyotani et al.,581 who performed the thermal decomposition CVD assisted by an electrodeposited metal nanorod catalyst.
of propylene at 800 °C. Pyrolytic carbon deposition from Depending on the types of catalytic metals (Au, Ni, Cu, Co)
propylene resulted in carbon tubes within the pores of AAO, in and germane (GeH4) concentration during CVD, Ge nano-
which the wall thickness of the carbon tubes was dependent on wires or nanotubes could be synthesized at 310−370 °C. The
the deposition period. The carbon tubes obtained by the authors also demonstrated the synthesis of multi-segmented
method exhibited low crystalline quality. In another study, Chu nanowire junctions of Au1−xGex and Ge inside the nano-
et al.582 employed the pyrolytic carbon deposition method for channels of porous AAO template by Au nanorod-catalyzed
the preparation of carbon tubes, in which porous AAO VLS growth process from GeH4 precursor.598 Polycrystalline
membrane was exposed to either ethylene or pyrene gas CdS,599 In2O3,600 and ZnS601 nanotube arrays have also been
stream at 900 °C for 10 min. They showed that the synthesized within the pores of AAO membranes by low-
temperature needed for CVD of carbonaceous materials can temperature CVD methods using, respectively, cadmium
be lowered to 500 °C by decorating pore wall surfaces of AAO bis(diethyldithiocarbamate) [Cd(S2CNEt2)2] at 400 °C,
template with Ni-catalyst nanoparticles.582 Apart from lowering indium acetlacetonate [In(acac)3] at 350 °C, and zinc
the CVD temperature, it was also found that the metallic bis(diethyldithiocarbamate) [Zn(S2(NEt2)2] at 200 °C. Metal-
catalysts improve the crystalline quality of the resulting carbon catalyzed VLS growths of single crystalline CdS602 or ZnO603
nanostructures. Multiwalled carbon nanotubes (CNTs) embed- nanowires within the pores of AAO membrane have recently
ded in porous AAO have also been obtained by CVD of a been reported.
gaseous precursor (typically, acetylene) in the temperature
range of 550−650 °C in the presence of electrodeposited Co 9.8. Atomic Layer Deposition (ALD)
catalyst at the bottom of AAO pores (Figure 66).287,583−587 Atomic layer deposition (ALD) has drawn much attention as a
The ordered arrays of CNTs have been utilized as field versatile methodology for thin film deposition due to conformal
BC dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
Figure 65. Metal-assisted chemical etching of (100)-oriented silicon wafer by using ultrathin metal mesh for the preparation of SiNWs with
controlled axial orientation and morphology. Reproduced with permission from refs 575,576. Copyright 2011 The American Chemical Society.
nature, avoiding CVD-like film growth. By virtue of such a self-

terminating film growth process, the conformal and uniform
deposition of film with atomic scale precision is achievable over
a large area.
Ott et al.610 first performed ALD of Al2O3 on porous AAO
membrane to narrow the pores, and demonstrated the gas
separation capability of the pore-modulated AAO membrane.
In another study, Chen et al.611 reported a strategy for
fabricating a single-molecule (i.e., DNA molecule) sensor
through surface modification of the pore walls of AAO and
precise control of the pore diameter at the single angstrom
scale. Since then, ALD on porous AAO has been intensively
utilized as a facile method not only for surface modification of
oxide nanopores,612 but also for fabricating 1D functional
nanostructures, such as nanowires,613 nanorods,614,615 and
nanotubes.616−625
Single-614,616,624−628 or multi-layered617,621 nanotubes com-
posed of different materials can conveniently be fabricated
through a deliberate choice of precursor molecules during ALD
on the pore wall surfaces of AAO. The ability to precisely
control film thickness is beneficial in tuning the thickness of
tube walls and the gap between each tube. Fabrications of
multi-segmented nanotubes have also been demonstrated
Figure 66. (a) Schematic procedure for the fabrication of carbon
recently through the combination of 3D site-selective ALD
nanotubes (CNTs). (b) SEM image of the ordered arrays of CNT
fabricated by the method in (a). Reprinted with permission from ref and anodization of aluminum. Bae et al.618 have shown that
583. Copyright 1999 AIP Publishing LLC. cylindrical nanopores of AAO can be continuously anodized
upon coating with thin organic and/or inorganic layers such as
and uniform deposition of thin films on substrates with octadecyltrichlorosilane (OTS)-self-assembled monolayers and
complicated 3D morphology.143,604−609 In ALD, a thin film of a ALD-grown TiO2, ZnO, and ZrO2. Nanowires or nanorods can
desired material is grown in a layer-by-layer manner by also be obtained through the so-called “super-filling” of the
repeating a unit cycle composed of four consecutive steps: (i) pores of AAO by virtue of the superior capability of ALD
precursor exposure, (ii) purging (or evacuation) of unreacted techniques for conformal film deposition over other conven-
excess gas molecules and reaction byproducts, (iii) reactant tional thin film deposition techniques.613,615 3D device
exposure, and (iv) subsequent purging (Figure 68). Because of architectures can be realized by the ALD of appropriate
the alternating exposure of gaseous precursor and reactant at materials within pores of AAO, and the approach may be
the separate steps, the film growth process is self-limiting in its beneficial to energy storage and energy conversion systems
BD dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
Figure 67. (a−d) Schematic cross-sections, showing the growth of SiNWs in porous AAO using Au catalyst: (a) after pre-annealing at 900 °C, (b)
after HF etching to remove SiO2, (c) electroless deposition of Au catalyst, and (d) VLS growth of SiNWs. (e) Cross-sectional TEM image of a SiNW
in AAO template along the [011] zone axis. The dashed line shows the interface between the original Si(100) substrate and SiNW. The magnified
TEM image of the area marked with a white rectangle is shown in (f), which demonstrates homoepitaxial growth of SiNW. Reprinted with
permission from ref 592. Copyright 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
have been independently reported by Comstock et al.619 and

Lee et al.635 Comstock et al.619 reported a fabrication strategy
for a nanotubular glucose sensor by using ALD-grown Pt thin
films within the pores of AAO. Lee et al.635 realized fast
response H2 sensors by transferring TiO2-coated AAO onto a
glass substrate followed by selective removal of the AAO.
Nanotube arrays synthesized by a similar approach have been
used as an ultraviolet (UV) sensor,636 membranes for gas and
molecule separations,612,637,638 catalytic membranes,639,640 and
photocatalysts.641,642
10. CLOSING REMARKS AND OUTLOOK

The anodization of aluminum and the resulting porous anodic
aluminum oxide (AAO) are currently the subject of extensive
research with nearly a thousand papers published annually in
Figure 68. Schematic illustration of a typical atomic layer deposition the field. In this Review, we have presented fundamental
(ALD) process of Al2O3 ALD from trimethyl aluminum (TMA) and electrochemical processes associated with the porous-type
water (H2O). anodization of aluminum, the recent progress on aluminum
anodization for the fabrication of self-ordered porous AAO, and
such as Li batteries629−631 and solar cells.407,626 Banergee et applications of porous AAO to templated synthesis of
al.632 have recently demonstrated fabrication of densely packed functional nanostructures for current nanotechnology research.
3D nanocapacitors by performing the sequential ALD of a TiN Over the past near 100 years, many electrochemical aspects
bottom electrode (BE)/dielectric Al2O3/TiN top electrode of aluminum anodization have been disclosed. Ionic migrations
(TE) within the pores of AAO (Figure 69). Because of the large within the oxide have been explained in the framework of high-
interfacial area of TiN/Al2O3 inside the open volume of porous field conduction theory. The type of acid electrolytes and
AAO, their 3D nanocapacitors exhibited considerably higher anodizing potential have direct relevance not only on the
capacitance as compared to equivalent 2D planar capacitors: structural parameters (e.g., pore diameter, interpore distance,
∼100 μF cm−2 for 3D nanocapacitors formed in 10-μm-thick and the barrier layer thickness) of the porous AAO, but also on
AAO. the incorporation of anionic species and their distribution in
ALD-assisted modification of AAO surfaces has also been the anodic oxide. Empirical relations between the parameters
considered a promising approach to molecule and gas defining the geometric structure of porous AAO and the
sensing.619,633,634 Two different kinds of sensor configurations anodizing potential have also been established. Pore formation
BE dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
Figure 69. Arrays of supercapacitors fabricated by sequential ALD of TiN, Al2O3, and TiN within pores of AAO: (a) cross-sectional SEM images of
the capacitors at the pore mouth (upper panel) and at the pore bottom (lower panel) and (b) schematic drawing of a unit cell of the capacitor.
Reprinted with permission from ref 632. Copyright 2009 Macmillan Publishers Ltd.: Nature Nanotechnology.
has long been attributed to the field-assisted dissolution of pulse, cyclic, and guided anodization), the diameter, density,
anodic alumina. This dissolution-based pore formation model and aspect ratio of pores, and even internal pore structures can
appears to be operative for the initial stage of pore formation.
However, for steady-state pore formation, there is a growing be tightly controlled by appropriate selection of the anodizing
number of results from recent experiments and theoretical conditions. These capabilities may offer large degrees of
modelings, disproving the field-assisted oxide dissolution
freedom for the templated syntheses of low-dimensional
model. These include, for instance, the direct ejection of Al3+
ions from the metal/oxide interface through the barrier oxide to functional nanostructures, and also in the development of
the anodizing electrolyte (from 18O isotope studies) and the AAO-based advanced devices, allowing simple and cost-
viscous flow of oxide materials from the pore base toward the
cell boundary (from W-tracer studies and finite-elemental effective non-lithographic fabrication of extended arrays of
analysis). However, more systematic experimental investiga- structurally well-defined and identical nanostructures. Indeed,
tions using various electrolytes/tracer elements and theoretical over the last two decades, we have witnessed fascinating
modelings considering the mobility of tracer cations are
required to fully verify the oxide flow model. Furthermore, applications of porous AAO membranes as templates for the
recent studies have revealed that the pore initiation and self- synthesis of various nanowires and nanotubes, as masks for
organized formation of porous AAO need to be understood in
extended arrays of structurally well-defined surface nano-
terms of mechano-electrochemistry. Studies have indicated that
stresses and their gradients within anodic oxide have profound patterns, and also as platform materials for (bio) molecule
implications on ionic migration within the anodic oxide, on separations, catalysts, drug delivery, photonic, and energy
morphological instability associated with pore initiation at the
early stage of anodization, breakdown of growing oxide, as well storage devices. All of these applications have been achieved
as the viscous flow of oxide materials and self-organization of through deliberate control over the dimensions of pores and
pores during the steady-state anodic oxidation. Although some the thickness of AAO membranes, and also through the
progress in this direction has recently been made, satisfactory
correlation between stresses and all experimental observations appropriate engineering of surface properties of porous AAO. It
has yet to be achieved. Internal stresses of growing anodic oxide is very likely that evolving experimental techniques for
need to be systematically evaluated in situ under controlled engineering of the internal pore structures and for programmed
anodization conditions. In addition, the effect of external
stresses on the anodization kinetics as well as on the self- functionalizing of the surface properties of porous AAO will
ordering behavior of pores needs to be further investigated. further expand the application field. Accordingly, the future
Studies on these issues would do much to advance our
knowledge on the mechanism governing the self-organized prospects for nanotechnology applications of porous AAO are
formation of pores during anodization of aluminum. Thorough very promising.
understanding of the mechano-electrochemical processes may
provide a solid foundation for exploring new electrolyte AUTHOR INFORMATION
systems and novel porous architectures as well as for
developing ordered porous structures from other valve-metals, Corresponding Author
such as Mg, Zr, Nb, Sn, Hf, Ta, W, Bi, etc. *E-mail: [email protected].
Aluminum anodizing under properly controlled conditions Notes
produces highly ordered porous AAOs. On the basis of recent
developments of various anodization methods (e.g., mild, hard, The authors declare no competing financial interest.
BF dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
Biographies the former director of Max-Planck-Institut für Mikrostruktur-

physik in Halle, Germany.
ABBREVIATIONS
AAO anodic aluminum oxide
U anodizing potential
j current density
E electric field
E* threshold electric field
t+ cation transport number
t− anion transport number
ηj current efficiency (i.e., oxide formation
efficiency)
PBR Pilling−Bedworth ratio
ΔU potential drop
tb barrier layer thickness
Woo Lee is a principal researcher at Korea Research Institute of ν hopping attempt frequency
Standards and Science (KRISS) and a professor of the Department of ρ density of mobile charge in C cm−3
Nano Science, University of Science and Technology (UST), Korea. a hopping interdistance
He received his Ph.D. from Seoul National University (2003). He W hopping activation energy at zero field
worked with the late Prof. Ulrich Gösele as a postdoctoral research α parameter describing the asymmetry of the
fellow and later a group leader at Max-Planck-Institut fü r activation barrier at non-zero field
Mikrostrukturphysik in Halle, Germany, until he joined KRISS in z valence of the mobile ions
2008. He brought a renewed attention to the academic research on F Faraday’s constant
pulsed anodization as well as hard anodization of aluminum by Φm/o potential drop at the metal/oxide interface
establishing new self-ordering regimes and also by implementing them Φo/e potential drop at the oxide/electrolyte
for the structural engineering of porous AAO. His research interests interface
focus on the anodization of aluminum and template-based synthesis of RBS Rutherford backscattering spectrometry
low-dimensional functional nanostructures for memory and energy TEM transmission electron microscopy
harvesting applications. AR anodizing ratio (in nm V−1)
P porosity of porous AAO
μi ionic chemical potential
Ji flux of ion i
Ci concentration of ion i
uio pre-exponential velocity of ion i
a migration jump distance in the oxide
σ mean stress
ϕ electrical potential
uio standard chemical potential of ion i
zi charge number of ion i
Ωi molar volume of ion i
UB breakdown potential
ρe electrolyte resistivity
CA− anion concentration
EB electric breakdown
Sang-Joon Park did his graduate work in Materials Science & MB mechanical breakdown
Engineering at the Pohang University of Science and Technology UEB electric breakdown potential
(POSTECH) under the co-supervision of Woo Lee and Prof. Sunggi UMB mechanical breakdown potential
Baik. He earned his Ph.D. with a main focus on resistive switching of CB conduction band
capacitors with TiO2 active layer, grown by atomic layer deposition tox oxide thickness
(ALD) in 2014. He then joined Woo Lee’s group at KRISS as a je electronic current
postdoctoral researcher. His research interest is atomic layer x travel distance of electrons
deposition (ALD) for functional nanostructures. α(E) the impact ionization coefficient at the
electric field E
ψi the threshold energy for impact ionization
ACKNOWLEDGMENTS
r recombination constant (r < 1)
Support from KRISS project “Anodization Research Laboratory tox,B critical oxide thickness at the moment of
(KRISS-2013-13011082)” and in part from the “Future-based breakdown
Technology Development Program (Nano Fields)” through the T temperature
National Research Foundation of Korea (NRF) funded by the jt total current density
Ministry of Science, ICT, and Future Planning (Grant no. j1 oxidation current
2010-0029332) is greatly acknowledged. This Review is j2 current density consumed by the incorpo-
dedicated to the memory of the late Professor Ulrich Gösele, rated electrolyte species
BG dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX
γ the ratio j2/j1 EM elastic modulus of metal strip

ρox oxide density νM Poisson ratio of metal strip
M1 molecular weight of the oxide L metal strip length
M2 molecular weight of the species incorporated jlimit limiting current
into the oxide ΔK the substrate curvature in km−1
x1, x2 anion valences PSD power spectral density
y1, y2 cation valences 1D one dimension
K unitary rate of anodization for oxide without 2D two dimension
electrolyte incorporation 3D three dimension
φ ratio of the equivalent weight of the R radius curvature of the metal/oxide interface
incorporated species to that of oxide, that w angle subtended from the center of curvature
is, φ = (M2/x2y2)/(M1/x1y1) to the pore bases
C electrolyte concentrations jtot total ionic current density
ΔP stress accumulated in the oxide jox current density linked with the number of
ε oxide permittivity oxygen in porous AAO
γ surface tension jloss current density due to the loss of Al3+ ions
ΓA− anion density at the oxide surface at the into the electrolyte
breakdown potential (UB) jAl current density caused by direct ejection of
Qc total charge Al3+ ions
Dint interpore distance jdec current density stemming from the outward
Dp pore diameter movement of Al 3+ ions produced by
tw pore wall thickness decomposition inside the barrier oxide
ρp pore density toward the electrolyte
ζp ratio of the pore diameter (Dp) to the λc critical wavelength
anodization potential (=Dp/U) γ surface energy
MA mild anodization M biaxial modulus of solid
HA hard anodization UMA mild anodization potential
PA pulse anodization UHA hard anodization potential
CA cyclic anodization ΔU UHA − UMA
ζMA proportionality constant between Dint and MA-AAO AAO formed by mild anodization (MA)
mild anodization (MA) potential (UMA) HA-AAO AAO formed by hard anodization (HA)
ARMA anodizing ratio for mild anodization (MA) DMAint interpore distance of MA-AAO
ARHA anodizing ratio for hard anodization (HA) DMAint interpore distance of HA-AAO
PL photoluminescence DMAp pore diameter of MA-AAO
tetch pore wall etching time tMA
b barrier layer thickness of MA-AAO
EXAFS extended X-ray absorption fine structure tHA
b barrier layer thickness of HA-AAO
NMR nuclear magnetic resonance PMA porosity of MA-AAO
XRD X-ray diffraction PHA porosity of HA-AAO
TG thermogravimetry ζHA proportionality constant between Dint and
DSC differential scanning calorimetry hard anodization (HA) potential (U)
MS mass spectrometry τHA pulse duration for hard anodization (HA)
Vox molar volume of oxide grown during the Q Joule’s heat
anodization Rb resistance of the barrier layer
Vm molar volume of metal consumed during the TA transition between mild and hard anodiza-
anodization tion
n number of atoms of metal per one formula ITO indium tin oxide
of the oxide CNT carbon nanotube
ρm density of metal EDS energy dispersive X-ray spectroscopy
ρox density of oxide EBL electron beam lithography
ρAAO density of anodic aluminum oxide (AAO) LIL laser interference lithography
kV thickness ratio of the AAO formed during FIB focused-ion-beam
anodization to the aluminum consumed SPM scanning probe microscope
during anodization NSL nanosphere lithography
hAAO vertical height of the AAO PDMS poly-dimethylsiloxane
hAl vertical height of the aluminum consumed NIL nanoimprint lithography
during anodization RD-WETS reaction-diffusion wet-stamping
kv volume expansion factor SFIL step and flash imprint lithography
σ⊥ compressive stress normal to the oxide ECD electrochemical deposition
surface ALD atomic layer deposition
σES electrostatic stress CVD chemical vapor deposition
ε0 vacuum permittivity PVD physical vapor deposition
Y Yong’s modulus RIE reactive ion etching
Δk radius of curvature MTJ molecular transport junction
BH dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

OWL on-wire lithography S spreading parameter

Ppy polypyrole γsg solid−gas interfacial tensions
GMR giant magnetoresistance γsl solid−liquid interfacial tensions
NP nanoparticle γlg liquid−gas interfacial tensions
SAPT 2-(succinic anhydride)propyl trimethoxysi- θe finite contact angle
lane PVDF poly(vinylidene difluoride)
CTAB cetyltrimethylammonium bromide PEEK polyether ether ketone
TEOS tetraethoxylsilane PTFE polytetrafluoroethylene
Pluronic P123 poly(ethylene oxide) 20 -poly(propylene PDLLA poly(D,L-lactide)
oxide)70-poly(ethylene oxide)20 EBDW electron-beam direct writing
Brij 56 decaethylene glycol hexadecyl ether PMMA poly(methyl methacrylate)
S-helix single helix PS polystyrene
D-helix double helix PLD pulsed laser deposition
APTMS 3-aminoproyl trimethoxysilane MBE molecular-beam epitaxy
APTES 3-aminopropyl triethosysilane VLS vapor−liquid−solid
PFPES pentafluorophenyldimethylchlorosilane SiNW Si nanowire
PFPTES pentafluorophenyldimethylpropylchlorosi- MOCVD metallorganic chemical vapor deposition
lane TMA trimethyl aluminum
PEGS N-triethoxysilylpropyl-O-poly(ethylene OTS octadecyltrichlorosilane
oxide) urethane BE bottom electrode
PDDA poly(diallydimethylammonium chloride) TE top electrode
NPNT nanoparticle-decorate nanotubes UV ultraviolet
CYP2E1 cytochrome P450 2E1
G6PD glucose-6-phosphate dehydrogenase
NADPH nicotinamide adenine dinucleotide phos- REFERENCES
phate (1) Buff, H. Liebigs Ann. Chem. 1857, 3, 265.
NADP+ 2-oxoaldehyde dehydrogenas (2) Bengough, G. D.; Stuart, J. M. Improved process of protecting
RGDC arginine-glycine-aspartic acid-cysteine surfaces of aluminium of aluminium alloys. U.K. Patent 223,994,
PNIPAM poly(N-isopropylacrylamide) August 2, 1923.
BBIB 2-bromoisobutyryl bromide (3) Diggle, J. W.; Downie, T. C.; Goulding, C. W. Chem. Rev. 1969,
69, 365.
NIPAM N-isopropylacrylamide (4) Sheasby, P. G.; Pinner, R. The Surface Treatment and Finishing of
ATRP atom-transfer radical polymerization Aluminum and Its Alloys, 6th ed.; Finishing Publications Ltd. & ASM
PNIPAM-g-AAO PNIPAM-grafted AAO membrane International: Materials Park, OH, and Stevenage, UK, 2001.
LCST lower critical solution temperature (5) Masuda, H.; Fukuda, K. Science 1995, 268, 1466.
PHEMA poly(2-hydroxyethyl methacrylate) (6) Masuda, H.; Satoh, M. Jpn. J. Appl. Phys. 1996, 35, L126.
NTA-M2+ nitrilotriacetate-M2+, where M is Cu or Ni (7) Keller, F.; Hunter, M. S.; Robinson, D. L. J. Electrochem. Soc.
PEGDMA poly(ethylene glycol dimetrhacrylate) 1953, 100, 411.
VOC volatile organic compound (8) Despić, A. R. J. Electroanal. Chem. 1985, 191, 417.
PEG poly(ethylene glycol) (9) Takahashi, H.; Saito, Y.; Nagayama, M. J. Surf. Finish. Soc. Jpn.
PEG-g-AAO poly(ethylene glycol) (PEG) grafted AAO 1982, 33, 225.
(10) Thompson, G. E. Thin Solid Films 1997, 297, 192.
CS chitosan (11) Nishinaga, O.; Kikuchi, T.; Natsui, S.; Suzuki, R. O. Sci. Rep.
GPTMS 3-glycidoxypropyl trimethoxysilane 2013, 3, 2748.
PAA poly(arcrylic acid) (12) Kape, J. M. Electroplat. Met. Finish. 1961, 14, 407.
EIS electrochemical impedance spectroscopy (13) Furneaux, R. C.; Rigby, W. R.; Davidson, A. P. Nature 1989,
LbL layer-by-layer 337, 147.
PEI poly(ethylenimine) (14) Thompson, G. E.; Wood, G. C. Nature 1981, 290, 230.
PAH poly(allylamine hydrochloride) (15) Kape, J. M. Metallugia 1959, 60, 181.
PDADMAC poly(diallydimethylammonium chloride) (16) Lee, W.; Nielsch, K.; Gösele, U. Nanotechnology 2007, 18,
PSS poly(styrenesulfonate) 475713.
PVS poly(vinylsulfate) (17) Ono, S.; Saito, M.; Asoh, H. Electrochim. Acta 2005, 51, 827.
(18) Chu, S. Z.; Wada, K.; Inoue, S.; Isogai, M.; Katsuta, Y.;
QD quantum dot Yasumori, A. J. Electrochem. Soc. 2006, 153, B384.
SSM solid supported membranes (19) Mozalev, A.; Surganov, A.; Magaino, S. Electrochim. Acta 1999,
BLM black lipid membranes 44, 3891.
MPA 3-mercaptopropionic acid (20) Mozalev, A.; Mozaleva, I.; Sakairi, M.; Takahashi, H. Electrochim.
DODAB N,N-dimethyl-N,N dioctadecylammonium Acta 2005, 50, 5065.
bromide (21) Güntherschulz, A.; Betz, H. Z. Phys. 1934, 92, 367.
DPhPC 1,2-diphytanoyl-sn-glycero-3-phosphocholin (22) Verwey, J. W. Physica 1935, 2, 1059.
DPPTE 1,2-diphytano-dipalmitoyl-sn-glycero-s-phos- (23) Mott, N. F. Trans. Faraday Soc. 1947, 43, 429.
phothioethanol (24) Cabrera, N.; Mott, N. F. Rep. Prog. Phys. 1948, 12, 163.
GUV giant unilamellar vesicle (25) Lohrengel, M. M. Mater. Sci. Eng., R 1993, 11, 243.
(26) Davies, J. A.; Domeij, B.; Pringle, J. P. S.; Brown, F. J.
SPR surface plasmon resonance
Electrochem. Soc. 1965, 112, 675.
EPR electron paramagnetic resonance (27) Davies, J. A.; Pringle, J. P. S.; Graham, R. L.; Brown, F. J.
PAN polyacrylonitril Electrochem. Soc. 1962, 109, 999.
BI dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

(28) Shimizu, K.; Thompson, G. E.; Wood, G. C.; Xu, Y. Thin Solid (74) Di Quarto, F.; Piazza, S.; Sunseri, C. J. Electroanal. Chem. 1988,
Films 1982, 88, 255. 248, 99.
(29) Cherki, C.; Siejka, J. J. Electrochem. Soc. 1973, 120, 784. (75) Di Quarto, F.; Piazza, S.; Sunseri, C. J. Electrochem. Soc. 1984,
(30) Siejka, J.; Ortega, C. J. Electrochem. Soc. 1977, 124, 883. 131, 2901.
(31) Wu, Z.; Richter, C.; Menon, L. J. Electrochem. Soc. 2007, 154, E8. (76) Yahalom, J.; Hoar, T. P. Electrochim. Acta 1970, 15, 877.
(32) Skeldon, P.; Thompson, G. E.; Garcia-Vergara, S. J.; Iglesias- (77) Kato, M.; Uchida, E.; Kudo, T. J. Met. Finish. Soc. Jpn. 1984, 35,
Bubianes, L.; Blanco-Pinzon, C. E. Electrochem. Solid-State Lett. 2006, 475.
9, B47. (78) Arifuku, F.; Yoneyama, H.; Tamura, H. Electrochim. Acta 1980,
(33) Shimizu, K.; Kobayashi, K.; Thompson, G. E.; Wood, G. C. 25, 863.
Philos. Mag. A 1992, 66, 643. (79) Albella, J. M.; Montero, I.; Martínez-Duart, J. M. J. Electrochem.
(34) Shimizu, K.; Kobayahi, K.; Thompson, G. E.; Wood, G. C. J. Soc. 1984, 131, 1101.
Surf. Finish. Soc. Jpn. 1991, 42, 645. (80) Albella, J. M.; Montero, I.; Martínez-Duart, J. M. Thin Solid
(35) Güntherschulz, A.; Betz, H. Z. Phys. 1932, 68, 145. Films 1985, 125, 57.
(36) Dewald, J. F. Acta Metall. 1954, 2, 340. (81) Albella, J. M.; Montero, I.; Martínez-Duart, J. M. Electrochim.
(37) Dewald, J. F. J. Electrochem. Soc. 1955, 102, 1. Acta 1987, 32, 255.
(38) Chao, C. Y.; Lin, L. F.; Macdonald, D. D. J. Electrochem. Soc. (82) Zahavi, J.; Yahalom, J. Electrochim. Acta 1971, 16, 89.
1981, 128, 1187. (83) Di Quarto, F.; Piazza, S.; Sunseri, C. Corros. Sci. 1986, 26, 213.
(39) Olsson, C.-O. A.; Hamm, D.; Landolt, D. J. Electrochem. Soc. (84) Dyer, C. K.; Leach, J. S. L. J. Electrochem. Soc. 1978, 125, 1032.
2000, 147, 4093. (85) Jouve, G.; Derradji, N. E. J. Less-Common Met. 1982, 86, 161.
(40) Brown, F.; Mackintosh, W. D. J. Electrochem. Soc. 1973, 120, (86) Vermilyea, D. A. Acta Metall. 1954, 2, 476.
1096. (87) Albella, J. M.; Montero, I.; Martínez-Duart, J. M.; Parkhutik, V.
(41) Su, Z.; Bühl, M.; Zhou, W. J. Am. Chem. Soc. 2009, 131, 8697. J. Mater. Sci. 1991, 26, 3422.
(42) Davies, J. A.; Domeij, B. J. Electrochem. Soc. 1963, 110, 849. (88) Yahalom, J.; Zahavi, J. Electrochim. Acta 1971, 16, 603.
(43) Khalil, N.; Leach, J. S. L. Electrochim. Acta 1986, 31, 1279. (89) Ikonopisov, S.; Girginov, A.; Machkova, M. Electrochim. Acta
(44) Thompson, G. E.; Xu, Y.; Skeldon, P.; Shimizu, K.; Han, S. H.; 1977, 22, 1283.
Wood, G. C. Philos. Mag. B 1987, 55, 651. (90) Ikonopisov, S. Electrochim. Acta 1977, 22, 1077.
(45) Dekker, A.; Middelhoek, A. J. Electrochem. Soc. 1970, 117, 440. (91) Nigam, R. K.; Singh, K. C.; Maken, S. Thin Solid Films 1987,
(46) Takahashi, H.; Nagayama, M. Corros. Sci. 1978, 18, 911. 155, 115.
(47) Houser, J. E.; Hebert, K. R. Phys. Status Solidi A 2008, 205, (92) Ikonopisov, S. Electrochim. Acta 1969, 14, 761.
2396. (93) Ikonopisov, S.; Elenkov, N. J. Electroanal. Chem. 1978, 86, 105.
(48) Hebert, K. R.; Houser, J. E. J. Electrochem. Soc. 2009, 156, C275. (94) Shimizu, K. Electrochim. Acta 1981, 26, 1691.
(49) Battaglia, V.; Newman, J. J. Electrochem. Soc. 1995, 142, 1423. (95) Albella, J. M.; Montero, I.; Fernandez, M.; Gomez-Aleixandre,
(50) Bradhurst, D. H.; Leach, J. S. L. J. Electrochem. Soc. 1966, 113, C.; Martínez-Duart, J. M. Electrochim. Acta 1985, 30, 1361.
1245. (96) Montero, I.; Albella, J. M.; Martínez-Duart, J. M. J. Electrochem.
(51) Tajima, S.; Shimizu, K.; Baba, N.; Matsuzawa, S. Electrochim. Soc. 1985, 132, 814.
Acta 1977, 22, 845. (97) Sato, N. Electrochim. Acta 1971, 16, 1683.
(52) Tajima, S. Electrochim. Acta 1977, 22, 995. (98) Garcia-Vergara, S. J.; Skeldon, P.; Thompson, G. E.; Habazaki,
(53) Shimizu, K.; Tajima, S. Electrochim. Acta 1980, 25, 259. H. Electrochim. Acta 2006, 52, 681.
(54) Kasalica, B.; Belča, I.; Stojadinović, S.; Sarvan, M.; Perić, M.; (99) Sulka, G. D. Highly ordered anodic porous alumina formation
Zeković, L. J. Phys. Chem. C 2007, 111, 12315. by self-organized anodizing. In Nanostructured Materials in Electro-
(55) Stojadinović, S.; Belča, I.; Kasalica, B.; Zeković, L.; Tadic, M. chemistry; Eftekhari, A., Ed.; Wiley-VCH Verlag GmbH & Co. KGaA:
Electrochem. Commun. 2006, 8, 1621. Weinheim, 2008; pp 8−20.
(56) Ikonopisov, S. Electrochim. Acta 1975, 20, 783. (100) O’Sullivan, J. P.; Wood, G. C. Proc. R. Soc. London, Ser. A 1970,
(57) Kasalica, B.; Stojadinović, S.; Zeković, L.; Belča, I.; Nikolic, D. 317, 511.
Electrochem. Commun. 2005, 7, 735. (101) Parkhutik, V. P.; Shershulsky, V. I. J. Phys. D: Appl. Phys. 1992,
(58) Stojadinović, S.; Belča, I.; Zeković, L.; Kasalica, B.; Nikolic, D. 25, 1258.
Electrochem. Commun. 2004, 6, 1016. (102) Sulka, G. D.; Parkoła, K. G. Electrochim. Acta 2007, 52, 1880.
(59) Stojadinović, S.; Zeković, L.; Belča, I.; Kasalica, B. Electrochem. (103) Lee, W.; Kim, J.-C.; Gösele, U. Adv. Funct. Mater. 2010, 20, 21.
Commun. 2004, 6, 427. (104) Ebihara, K.; Takahashi, H.; Nagayama, M. J. Met. Finish. Soc.
(60) Vermilyea, D. A. J. Electrochem. Soc. 1957, 104, 542. Jpn. 1983, 34, 548.
(61) Jackson, N. F. J. Appl. Electrochem. 1973, 3, 91. (105) Ebihara, K.; Takahashi, H.; Nagayama, M. J. Met. Finish. Soc.
(62) Habazaki, H.; Ogasawara, T.; Konno, H.; Shimizu, K.; Nagata, Jpn. 1982, 33, 156.
S.; Skeldon, P.; Thompson, G. E. Corros. Sci. 2007, 49, 580. (106) Li, A. P.; Müller, F.; Birner, A.; Nielsch, K.; Gösele, U. J. Appl.
(63) Habazaki, H.; Uozumi, M.; Konno, H.; Shimizu, K.; Skeldon, P.; Phys. 1998, 84, 6023.
Thompson, G. E. Corros. Sci. 2003, 45, 2063. (107) Hwang, S.-K.; Jeong, S.-H.; Hwang, H.-Y.; Lee, O.-J.; Lee, K.-
(64) Yahalom, J.; Zahavi, J. Electrochim. Acta 1970, 15, 1429. H. Korean J. Chem. Eng. 2002, 19, 467.
(65) Leach, J. S. L.; Pearson, B. R. Corros. Sci. 1988, 28, 43. (108) Ono, S.; Masuko, N. Surf. Coat. Technol. 2003, 169−170, 139.
(66) Li, Y.; Shimada, H.; Sakairi, M.; Shigyo, K.; Takahashi, H.; Seo, (109) Nielsch, K.; Choy, J.; Schwirn, K.; Wehrspohn, R. B.; Gösele,
M. J. Electrochem. Soc. 1997, 144, 866. U. Nano Lett. 2002, 2, 677.
(67) Proost, J.; Vanhumbeeck, J.-F.; Van Overmeere, Q. Electrochim. (110) Chu, S.-Z.; Wada, K.; Inoue, S.; Isogai, M.; Yasumori, A. Adv.
Acta 2009, 55, 350. Mater. 2005, 17, 2115.
(68) Matykina, E.; Arrabal, R.; Skeldon, P.; Thompson, G. E.; (111) Lee, W.; Ji, R.; Gösele, U.; Nielsch, K. Nat. Mater. 2006, 5, 741.
Habazaki, H. Thin Solid Films 2008, 516, 2296. (112) Lee, W.; Schwirn, K.; Steinhart, M.; Pippel, E.; Scholz, R.;
(69) Ikonopisov, S.; Girginov, A.; Machkova, M. Electrochim. Acta Gösele, U. Nat. Nanotechnol. 2008, 3, 234.
1979, 24, 451. (113) Schwirn, K.; Lee, W.; Hillebrand, R.; Steinhart, M.; Nielsch, K.;
(70) Santway, R. W.; Alwitt, R. S. J. Electrochem. Soc. 1970, 117, 1282. Gösele, U. ACS Nano 2008, 2, 302.
(71) Burger, F. J.; Wu, J. C. J. Electrochem. Soc. 1971, 118, 2039. (114) Hunter, M. S.; Fowle, P. J. Electrochem. Soc. 1954, 101, 481.
(72) Wood, G. C.; Pearson, C. Corros. Sci. 1967, 7, 119. (115) Vrublevsky, I.; Parkoun, V.; Schreckenbach, J. Appl. Surf. Sci.
(73) Alwitt, R. S.; Vijh, A. K. J. Electrochem. Soc. 1969, 116, 388. 2005, 242, 333.
BJ dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

(116) Vrublevsky, I.; Parkoun, V.; Schreckenbach, J.; Marx, G. Appl. (152) Chang, Y.; Ling, Z.; Liu, Y.; Hu, X.; Li, Y. J. Mater. Chem. 2012,
Surf. Sci. 2004, 227, 282. 22, 7445.
(117) Vrublevsky, I.; Parkoun, V.; Sokol, V.; Schreckenbach, J. Appl. (153) Pilling, N. B.; Bedworth, R. E. J. Inst. Met. 1923, 29, 529.
Surf. Sci. 2005, 252, 227. (154) Phull, B. Evaluating stress-corrosion cracking. In ASM
(118) Li, Y.; Zheng, M.; Ma, L.; Shen, W. Nanotechnology 2006, 17, Handbook, Corrosion: Fundametals, Testing, and Protection; Cramer, S.
5101. D., Covino, B. S., Jr., Eds.; ASM International: Materials Park, OH,
(119) Schwirn, K. Harte Anodisation von Aluminium mit Verdünnter 2003; pp 575−616.
Schwefeläure. Ph.D. Thesis, Martin-Luther-Universität Halle-Witten- (155) Burgers, W. G.; Claasen, A.; Zernike, J. Z. Phys. 1932, 74, 593.
berg, Halle (Saale), 2008. (156) Bernard, W. J.; Cook, J. W. J. Electrochem. Soc. 1959, 106, 643.
(120) Yamamoto, Y.; Baba, N.; Tajima, S. Nature 1981, 289, 572. (157) Dorsely, G. A., Jr. J. Electrochem. Soc. 1969, 116, 466.
(121) Xu, W. L.; Zheng, M. J.; Wu, S.; Sheng, W. Z. Appl. Phys. Lett. (158) Garcia-Vergara, S. J.; Habazaki, H.; Skeldon, P.; Thompson, G.
2004, 85, 4364. E. Nanotechnology 2007, 18, 415605.
(122) Li, Y. B.; Zheng, M. J.; Ma, L. Appl. Phys. Lett. 2007, 91, (159) Garcia-Vergara, S. J.; Skeldon, P.; Thompson, G. E.; Habazaki,
073109. H. Corros. Sci. 2007, 49, 3696.
(123) Vojkuvka, L.; Santos, A.; Pallarès, J.; Ferrè-Borrull, J.; Marsal, (160) Mercier, D.; Van Overmeere, Q.; Santoro, R.; Proost, J.
L. F.; Celis, J. P. Surf. Coat. Technol. 2012, 206, 2115. Electrochim. Acta 2011, 56, 1329.
(124) Roa, J. J.; Gastón-García, B.; García-Lecina, E.; Müller, C. (161) Baron-Wiecheć, A.; Ganem, J. J.; Garcia-Vergara, S. J.; Skeldon,
Ceram. Int. 2012, 38, 1627. P.; Thompson, G. E.; Vickridge, I. C. J. Electrochem. Soc. 2010, 157,
(125) Thompson, G. E.; Wood, G. C. Anodic Films on Aluminium. C399.
In Treatise on Materials Science and Technology, Corrosion: Aqueous (162) Arurault, L. Trans. Inst. Met. Finish. 2008, 86, 51.
Process and Passivation; Scully, J. C., Ed.; Academic Press: New York, (163) Vrublevsky, I.; Parkoun, V.; Schreckenbach, J.; Marx, G. Appl.
1983; pp 286−287. Surf. Sci. 2003, 220, 51.
(126) Ono, S.; Ichinose, H.; Masuko, N. Corros. Sci. 1992, 33, 841. (164) Zhou, F.; Al-Zenati, A. K. M.; Baron-Wiecheć, A.; Curioni, M.;
(127) Mason, R. B. J. Electrochem. Soc. 1955, 102, 671. Garcia-Vergara, S. J.; Habazaki, H.; Skeldon, P.; Thompson, G. E. J.
(128) Wood, G. C.; Skeldon, P.; Thompson, G. E.; Shimizu, K. J. Electrochem. Soc. 2011, 158, C202.
Electrochem. Soc. 1996, 143, 74. (165) Jessensky, O.; Müller, F.; Gösele, U. Appl. Phys. Lett. 1998, 72,
(129) Han, H.; Park, S.-J.; Jang, J. S.; Ryu, H.; Kim, K. J.; Baik, S. ACS
1173.
Appl. Mater. Interfaces 2013, 5, 3441. (166) Surganov, V. F.; Mozalev, A. M.; Mozaleva, I. I. Russ. J. Appl.
(130) Thompson, G. E.; Furneaux, R. C.; Wood, G. C. Corros. Sci.
Chem. 1997, 70, 254.
1978, 18, 481.
(167) Vrublevsky, I.; Parkoun, V.; Sokol, V.; Schreckenbach, J.; Marx,
(131) Ono, S.; Masuko, N. Corros. Sci. 1992, 33, 503.
G. Appl. Surf. Sci. 2004, 222, 215.
(132) Ono, S.; Ichinose, H.; Kawaguchi, T.; Masuko, N. Corros. Sci.
(168) Li, F.; Zhang, L.; Metzger, R. M. Chem. Mater. 1998, 10, 2470.
1990, 31, 249.
(169) Nelson, J. C.; Oriani, R. A. Corros. Sci. 1993, 34, 307.
(133) Thompson, G. E.; Furneaux, R. C.; Wood, G. C. J. Electrochem.
(170) Vanhumbeeck, J.-F.; Proost, J. Electrochim. Acta 2008, 53,
Soc. 1978, 125, 1480.
6165.
(134) Thornton, M. C.; Furneaux, R. C. J. Mater. Sci. Lett. 1991, 10,
(171) Stoney, G. G. Proc. R. Soc. London, Ser. A 1909, 82, 172.
622.
(172) Vermilyea, D. A. J. Electrochem. Soc. 1963, 110, 345.
(135) Le Coz, F.; Arurault, L.; Data, L. Mater. Charact. 2010, 61, 283.
(173) Moon, S.-M.; Pyun, S.-I. J. Solid State Electrochem. 1998, 2, 156.
(136) Oka, Y.; Takahashi, T.; Okada, K.; Iwai, S.-i. J. Non-Cryst. Solids
(174) Moon, S.-M.; Pyun, S.-I. Electrochim. Acta 1998, 43, 3117.
1979, 30, 349.
(175) Van Overmeere, Q.; Blaffart, F.; Proost, J. Electrochem.
(137) El-Mashri, S. M.; Jones, R. G.; Forty, A. J. Philos. Mag. A 1983,
Commun. 2010, 12, 1174.
48, 665.
(176) Ç apraz, Ö . Ö .; Hebert, K. R.; Shrotriya, P. J. Electrochem. Soc.
(138) Farnan, I.; Dupree, R.; Forty, A. J.; Jeong, Y. S.; Thompson, G.
E.; Wood, G. C. Philos. Mag. Lett. 1989, 59, 189. 2013, 160, D501.
(139) Brown, I. W. M.; Bowden, M. E.; Kemmitt, T.; MacKenzie, K. (177) Van Overmeere, Q.; Proost, J. Electrochim. Acta 2010, 55, 4653.
J. D. Curr. Appl. Phys. 2006, 6, 557. (178) Van Overmeere, Q.; Proost, J. Electrochim. Acta 2011, 56,
(140) Kirchner, A.; MacKenzie, K. J. D.; Brown, I. W. M.; Kemmitt, 10507.
T.; Bowden, M. E. J. Membr. Sci. 2007, 287, 264. (179) Van Overmeere, Q.; Vanhumbeeck, J.-F.; Proost, J. Rev. Sci.
(141) Farnan, I.; Dupree, R.; Jeong, Y.; Thompson, G. E.; Wood, G. Instrum. 2010, 81, 045106.
C.; Forty, A. J. Thin Solid Films 1989, 173, 209. (180) Sulka, G. D.; Stroobants, S.; Moshchalkov, V. V.; Borghs, G.;
(142) Ingham, C. J.; ter Maat, J.; de Vos, W. M. Biotechnol. Adv. 2012, Celis, J.-P. J. Electrochem. Soc. 2004, 151, B260.
30, 1089. (181) Park, S.-H.; Lee, Y.; Lee, J.-K.; Kim, K.-B. Electrochem. Solid-
(143) Jani, A. M. M.; Losic, D.; Voelcker, N. H. Prog. Mater. Sci. State Lett. 2006, 9, D31.
2013, 58, 636. (182) Cojocaru, C. S.; Padovani, J. M.; Wade, T.; Mandoli, C.;
(144) Mardilovich, P. P.; Govyadinov, A. N.; Mukhurov, N. I.; Jaskierowicz, G.; Wegrowe, J. E.; i Morral, A. F.; Pribat, D. Nano Lett.
Rzhevskii, A. M.; Paterson, R. J. Membr. Sci. 1995, 98, 131. 2005, 5, 675.
(145) Levin, I.; Brandon, D. J. Am. Ceram. Soc. 1998, 81, 1995. (183) Xiang, Y.; Lee, W.; Nielsch, K.; Abstreiter, G.; i Morral, A. F.
(146) Burgos, N.; Paulis, M.; Montes, M. J. Mater. Chem. 2003, 13, Phys. Status Solidi RRL 2008, 2, 59.
1458. (184) Masuda, H.; Nishio, K.; Baba, N. Appl. Phys. Lett. 1993, 63,
(147) Le Coz, F.; Arurault, L.; Fontorbes, S.; Vilar, V.; Datas, L.; 3155.
Winterton, P. Surf. Interface Anal. 2010, 42, 227. (185) Gowtham, M.; Eude, L.; Cojocaru, C. S.; Marquardt, B.; Jeong,
(148) Ozao, R.; Ochiai, M.; Ichimura, N.; Takahashi, H.; Inada, T. H. J.; Legagneux, P.; Song, K. K.; Pribat, D. Nanotechnology 2008, 19,
Thermochim. Acta 2000, 353−354, 91. 035303.
(149) Bocchetta, P.; Sunseri, C.; Chiavarotti, G.; Quarto, F. D. (186) Oh, J.; Thompson, C. V. J. Electrochem. Soc. 2011, 158, C71.
Electrochim. Acta 2003, 48, 3175. (187) Hoar, T. P.; Yahalom, J. J. Electrochem. Soc. 1963, 110, 614.
(150) Mata-Zamora, M. E.; Saniger, J. M. Rev. Mex. Fis. 2005, 51, (188) Albella, J. M.; Montero, I.; Jimenez, M. C.; Martínez-Duart, J.
502. M. Electrochim. Acta 1991, 36, 739.
(151) McQuaig, M. K., Jr.; Toro, A.; Van Geertruyden, W.; Misiolek, (189) Van Overmeere, Q.; Mercier, D.; Santoro, R.; Proost, J.
W. Z. J. Mater. Sci. 2011, 46, 243. Electrochem. Solid-State Lett. 2012, 15, C1.
BK dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

(190) Van Overmeere, Q.; Nysten, B.; Proost, J. Appl. Phys. Lett. (230) Shingubara, S.; Morimoto, K.; Sakaue, H.; Takahagi, T.
2009, 94, 074103. Electrochem. Solid-State Lett. 2004, 7, E15.
(191) Garcia-Vergara, S. J.; Skeldon, P.; Thompson, G. E.; Habazaki, (231) Sun, C.; Luo, J.; Wu, L.; Zhang, J. ACS Appl. Mater. Interfaces
H. Corros. Sci. 2007, 49, 3772. 2010, 2, 1299.
(192) Singh, G. K.; Golovin, A. A.; Aranson, I. S. Phys. Rev. B 2006, (232) Ono, S.; Saito, M.; Ishiguro, M.; Asoh, H. J. Electrochem. Soc.
73, 205422. 2004, 151, B473.
(193) Hoar, T. P.; Mott, N. F. J. Phys. Chem. Solids 1959, 9, 97. (233) Chen, W.; Wu, J.-S.; Xia, X.-H. ACS Nano 2008, 2, 959.
(194) Hebert, K. R.; Albu, S. P.; Paramasivam, I.; Schmuki, P. Nat. (234) Martín, J.; Manzano, C. V.; Caballero-Calero, O.; Martín-
Mater. 2012, 11, 162. González, M. ACS Appl. Mater. Interfaces 2013, 5, 72.
(195) Raja, K. S.; Misra, M.; Paramguru, K. Electrochim. Acta 2005, (235) Su, Z.; Hähner, G.; Zhou, W. J. Mater. Chem. 2008, 18, 5787.
51, 154. (236) Su, Z.; Zhou, W. Adv. Mater. 2008, 20, 3663.
(196) Sample, C.; Golovin, A. A. Phys. Rev. E 2006, 74, 041606. (237) Su, Z.; Zhou, W. J. Mater. Chem. 2011, 21, 357.
(197) Stanton, L. G.; Golvin, A. A. Phys. Rev. B 2009, 79, 035414. (238) Hoar, T. P. Corros. Sci. 1967, 7, 341.
(198) Thamida, S. K.; Chang, H.-C. Chaos 2002, 12, 240. (239) Tu, G. C.; Chen, I. T.; Shimizu, K. J. Jpn. Inst. Light Met. 1990,
(199) Houser, J. E.; Hebert, K. R. J. Electrochem. Soc. 2006, 153, 40, 382.
B566. (240) Ono, S.; Saito, M.; Asoh, H. Electrochem. Solid-State Lett. 2004,
(200) Houser, J. E.; Hebert, K. R. Nat. Mater. 2009, 8, 415. 7, B21.
(201) Hunter, M. S.; Fowle, P. J. Electrochem. Soc. 1954, 101, 514. (241) Csokán, P. Trans. Inst. Met. Finish. 1964, 41, 51.
(202) Leach, J. S. L.; Neufeld, P. Corros. Sci. 1969, 9, 413. (242) Arrowsmith, D. J.; Clifford, A. W.; Moth, D. A. J. Mater. Sci.
(203) Nagayama, M.; Tamura, K. Electrochim. Acta 1968, 13, 1773. Lett. 1986, 5, 921.
(204) Chowdhury, P.; Thomas, A. N.; Sharma, M.; Barshilia, H. C. (243) Wada, K.; Shimohira, T.; Yamada, M.; Baba, N. J. Mater. Sci.
Electrochim. Acta 2014, 115, 657. 1986, 21, 3810.
(205) Singh, G. K.; Golovin, A. A.; Aranson, I. S.; Vinokur, V. M. (244) Kashi, M. A.; Ramazani, A.; Noormohammadi, M.; Zarei, M.;
Europhys. Lett. 2005, 70, 836. Marashi, P. J. Phys. D: Appl. Phys. 2007, 40, 7032.
(206) Friedman, A. L.; Brittain, D.; Menon, L. J. Chem. Phys. 2007, (245) Li, Y.; Ling, Z. Y.; Chen, S. S.; Wang, J. C. Nanotechnology
127, 154717. 2008, 19, 225604.
(207) Oh, J.; Thompson, C. V. Electrochim. Acta 2011, 56, 4044. (246) Srolovitz, D. J. Acta Metall. 1989, 37, 621.
(208) Baron-Wiecheć, A.; Burke, M. G.; Hashimoto, T.; Liu, H.; (247) Li, F. Nanostructure of anodic porous alumina films of interest
Skeldon, P.; Thompson, G. E.; Habazaki, H.; Ganem, J.-J.; Vickridge, I. in magnetic recording. Ph.D. Thesis, The University of Alabama, AL,
C. Electrochim. Acta 2013, 113, 302. 1998.
(209) Garcia-Vergara, S. J.; Clere, D. L.; Hashimoto, T.; Habazaki, (248) Gill, V.; Guduru, P. R.; Sheldon, B. W. Int. J. Solids Struct. 2008,
H.; Skeldon, P.; Thompson, G. E. Electrochim. Acta 2009, 54, 6403. 45, 943.
(210) Garcia-Vergara, S. J.; Skeldon, P.; Thompson, G. E.; Habazaki, (249) Matthias, S.; Schilling, J.; Nielsch, K.; Müller, F.; Wehrspohn,
H. Appl. Surf. Sci. 2007, 254, 1534. R. B.; Gösele, U. Adv. Mater. 2002, 14, 1618.
(211) Habazaki, H.; Shimizu, K.; Skeldon, P.; Thompson, G. E.; (250) He, B.; Son, S. J.; Lee, S. B. Langmuir 2006, 22, 8263.
(251) Brunker, S. E.; Cederquist, K. B.; Keating, C. D. Nanomedicine
Wood, G. C. J. Electrochem. Soc. 1996, 143, 2465.
2007, 2, 695.
(212) Habazaki, H.; Shimizu, K.; Skeldon, P.; Thompson, G. E.;
(252) Matthias, S.; Muller, F. Nature 2003, 424, 53.
Wood, G. C.; Zhou, X. Trans. Inst. Met. Finish. 1997, 75, 18.
(253) Casanova, F.; Chiang, C. E.; Li, C.-P.; Schuller, I. K. Appl. Phys.
(213) Garcia-Vergara, S. J.; Hashimoto, T.; Skeldon, P.; Thompson,
Lett. 2007, 91, 243103.
G. E.; Habazaki, H. Electrochim. Acta 2009, 54, 3662. (254) Bruschi, L.; Mistura, G.; Liu, L.; Lee, W.; Gösele, U.; Coasne,
(214) Iglesias-Rubianes, L.; Skeldon, P.; Thompson, G. E.; Habazaki,
B. Langmuir 2010, 26, 11894.
H.; Shimizu, K. J. Electrochem. Soc. 2002, 149, B23. (255) Miller, M. A. Anodizing process and system. U.S. Patent
(215) Pringle, J. P. S. Electrochim. Acta 1980, 25, 1423. 2,920,018, January 5, 1960.
(216) Garcia-Vergara, S. J.; Skeldon, P.; Thompson, G. E.; Habazaki, (256) Schaedel, F. C. Aluminum anodizing method. U.S. Patent
H. Surf. Interface Anal. 2007, 39, 860. 3,418,222, December 24, 1968.
(217) Bolger, C. T.; Fois, G.; Petkov, N.; Sassiat, N.; Burke, M.; (257) Yokoyama, K.; Konno, H.; Takahashi, H.; Nagayama, M. Plat.
Quinn, A. J.; Cross, G. L. W.; Holmes, J. D. Nanotechnology 2012, 23, Surf. Finish. 1982, 7, 62.
175602. (258) Tu, G. C.; Huang, L. Y. Trans. Inst. Met. Finish. 1987, 65, 60.
(218) Garcia-Vergara, S. J.; Skeldon, P.; Thompson, G. E.; Habazaki, (259) Raj, V.; Rajaram, M. P.; Balasubramanian, G.; Vincent, S.;
H. Corros. Sci. 2008, 50, 3179. Kanagaraj, D. Trans. Inst. Met. Finish. 2003, 81, 114.
(219) Forgazza, M.; Santamaria, M.; Di Quarto, F.; Garcia-Vergara, S. (260) Murphy, J. F.; Michelson, C. E. A Theory for the Formation of
J.; Molchan, I.; Skeldon, P.; Thompson, G. E.; Habazaki, H. Anodic Oxide Coatings on Aluminium. Proceedings of Anodizing
Electrochim. Acta 2009, 54, 1070. Aluminium; Nottingham, England, 1961; pp 83−95.
(220) Herrera-Erazo, A. E.; Habazaki, H.; Shimizu, K.; Skeldon, P.; (261) Takahashi, H.; Nagayama, M.; Akahori, H.; Kitahara, A. J.
Thompson, G. E. Corros. Sci. 2000, 42, 1823. Electron Microsc. 1973, 22, 149.
(221) Csokán, P. Metalloberfläche 1961, 15, B49. (262) Rasmussen, J. Plat. Surf. Finish. 2001, 88, 42.
(222) Csokán, V. P.; Holló, M. Werkst. Korros. 1961, 12, 288. (263) Lee, W.; Scholz, R.; Gösele, U. Nano Lett. 2008, 8, 2155.
(223) Csokán, P.; Sc., C. C. Electroplat. Met. Finish. 1962, 15, 75. (264) Lee, W.; Kim, J.-C. Nanotechnology 2010, 21, 485304.
(224) Lee, W. JOM 2010, 62, 57. (265) Losic, D.; Lillo, M.; Losic, D., Jr. Small 2009, 5, 1392.
(225) Schwartz, G. C.; Platter, V. J. Electrochem. Soc. 1975, 122, 1508. (266) Losic, D.; Losic, D., Jr. Langmuir 2009, 25, 5426.
(226) Hillebrand, R.; Muller, F.; Schwirn, K.; Lee, W.; Steinhart, M. (267) Wang, B.; Xu, G.; Cui, P. Mater. Lett. 2013, 93, 336.
ACS Nano 2008, 2, 913. (268) Yang, C.-J.; Liang, S.-W.; Wu, P.-W.; Chen, C.; Shieh, J.-M.
(227) Masuda, H.; Hasegawa, E.; Ono, S. J. Electrochem. Soc. 1997, Electrochem. Solid-State Lett. 2007, 10, C69.
144, L127. (269) Miney, P. G.; Colavita, P. E.; Schiza, M. V.; Priore, R. J.;
(228) Zhang, L.; Cho, H. S.; Li, F.; Metzger, R. M.; Doyle, W. D. J. Haibach, F. G.; Myrick, M. L. Electrochem. Solid-State Lett. 2003, 6,
Mater. Sci. Lett. 1998, 17, 291. B42.
(229) Masuda, H.; Yada, K.; Osaka, A. Jpn. J. Appl. Phys. 1998, 37, (270) Rabin, O.; Herz, P. R.; Lin, Y.-M.; Akinwande, A. I.; Cronin, S.
L1340. B.; Dresselhaus, M. S. Adv. Funct. Mater. 2003, 13, 631.
BL dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

(271) Crouse, D.; Lo, Y.-H.; Miller, A. E.; Crouse, M. Appl. Phys. Lett. (307) Mozalev, A.; Sakairi, M.; Takahashi, H. J. Electrochem. Soc.
2000, 76, 49. 2004, 151, F257.
(272) Asoh, H.; Matsuo, M.; Yoshihama, M.; Ono, S. Appl. Phys. Lett. (308) Masuda, H.; Yamada, H.; Satoh, M.; Asoh, H.; Nakao, M.;
2003, 83, 4408. Tamamura, T. Appl. Phys. Lett. 1997, 71, 2770.
(273) Shiraki, H.; Kimura, Y.; Ishii, H.; Ono, S.; Itaya, K.; Niwano, M. (309) Masuda, H.; Asoh, H.; Watanabe, M.; Nishio, K.; Nakao, M.;
Appl. Surf. Sci. 2004, 237, 369. Tamamura, T. Adv. Mater. 2001, 13, 189.
(274) Tian, M.; Xu, S.; Wang, J.; Kumar, N.; Wertz, E.; Li, Q.; (310) Asoh, H.; Nishio, K.; Nakao, M.; Yokoo, A.; Tamamura, T.;
Campbell, P. M.; Chan, M. H. W.; Mallouk, T. E. Nano Lett. 2005, 5, Masuda, H. J. Vac. Sci. Technol., B 2001, 19, 569.
697. (311) Masuda, H.; Yotsuya, M.; Asano, M.; Nishio, K.; Nakao, M.;
(275) Kokonou, M.; Nassiopoulou, A. G.; Giannakopoulos, K. P. Yokoo, A.; Tamamura, T. Appl. Phys. Lett. 2001, 78, 826.
Nanotechnology 2005, 16, 103. (312) Smith, J. T.; Huang, Q.; Franklin, A. D.; Janes, D. B.; Sands, T.
(276) Seo, H.-S.; Jung, Y.-G.; Jee, S.-W.; Yang, J. M.; Lee, J.-H. Scr. D. Appl. Phys. Lett. 2008, 93, 043108.
Mater. 2007, 57, 968. (313) Jones, M. R.; Osberg, K. D.; Macfarlane, R. J.; Langille, M. R.;
(277) Chen, P.-L.; Kuo, C.-T.; Tsai, T.-G.; Wu, B.-W.; Hsu, C.-C.; Mirkin, C. A. Chem. Rev. 2011, 111, 3736.
Pan, F.-M. Appl. Phys. Lett. 2003, 82, 2796. (314) Mikulskas, I.; Juodkazis, S.; Tomašiunas,
̅ R.; Dumas, J. G. Adv.
(278) Sander, M. S.; Tan, L.-S. Adv. Funct. Mater. 2003, 13, 393. Mater. 2001, 13, 1574.
(279) Choi, J.; Sauer, G.; Göring, P.; Nielsch, K.; Wehrspohn, R. B.; (315) Choi, J.; Nielsch, K.; Reiche, M.; Wehrspohn, R. B.; Gösele, U.
Gösele, U. J. Mater. Chem. 2003, 13, 1100. J. Vac. Sci. Technol., B 2003, 21, 763.
(280) Zhao, X.; Lee, U.-J.; Seo, S.-K.; Lee, K.-H. Mater. Sci. Eng., C (316) Fournier-Bidoz, S.; Kitaev, V.; Routkevitch, D.; Manners, I.;
2009, 29, 1156. Ozin, G. A. Adv. Mater. 2004, 16, 2193.
(281) Yang, Y.; Chen, H.; Mei, Y.; Chen, J.; Wu, X.; Bao, X. Solid (317) Lee, W.; Ji, R.; Ross, C. A.; Gösele, U.; Nielsch, K. Small 2006,
State Commun. 2002, 123, 279. 2, 978.
(282) Yasui, N.; Imada, A.; Den, T. Appl. Phys. Lett. 2003, 83, 3347. (318) Matsui, Y.; Nishio, K.; Masuda, H. Small 2006, 2, 522.
(283) Crouse, M. M.; Miller, A. E.; Crouse, D. T.; Ikram, A. A. J. (319) Liu, C. Y.; Datta, A.; Wang, Y. L. Appl. Phys. Lett. 2001, 78,
Electrochem. Soc. 2005, 152, D167. 120.
(284) Vorobyova, A. I.; Outkina, E. A. Thin Solid Films 1998, 324, 1. (320) Masuda, H.; Kanezawa, K.; Nishio, K. Chem. Lett. 2002, 31,
(285) Mozalev, A.; Surganov, A.; Magaino, S. Electrochim. Acta 1999, 1218.
44, 3891. (321) Sun, Z.; Kim, H. K. Appl. Phys. Lett. 2010, 81, 3458.
(286) Mozalev, A.; Khatko, V.; Bittencourt, C.; Hassel, A. W.; (322) Kim, B.; Park, S.; McCarthy, T. J.; Russell, T. P. Small 2007, 3,
Gorokh, G.; Llobet, E.; Correig, X. Chem. Mater. 2008, 20, 6482. 1869.
(287) Iwasaki, T.; Motoi, T.; Den, T. Appl. Phys. Lett. 1999, 75, 2044. (323) Lipson, A. L.; Comstock, D. J.; Hersam, M. C. Small 2009, 5,
(288) Chu, S.-Z.; Wada, K.; Inoue, S.; Segawa, H. J. Electrochem. Soc. 2807.
2011, 158, C148. (324) Lai, K.-L.; Hon, M.-H.; Leu, I.-C. Nanoscale Res. Lett. 2011, 6,
(289) Oh, J.; Thompson, C. V. Adv. Mater. 2008, 20, 1368. 157.
(290) Oh, J.; Shin, Y. C.; Thompson, C. V. J. Electrochem. Soc. 2011, (325) Oshima, H.; Kikuchi, H.; Nakao, H.; Itoh, K.-i.; Kamimura, T.;
158, K11. Morikawa, T.; Matsumoto, K.; Umada, T.; Tamura, H.; Nishio, K.;
(291) Chu, S. Z.; Wada, K.; Inoue, S.; Todoroki, S. J. Electrochem. Soc. Masuda, H. Appl. Phys. Lett. 2007, 91, 022508.
2002, 149, B321. (326) Kustandi, T. S.; Loh, W. W.; Gao, H.; Low, H. Y. ACS Nano
(292) Chu, S. Z.; Wada, K.; Inoue, S.; Todoroki, S. Electrochim. Acta 2010, 4, 2561.
2003, 48, 3147. (327) Masuda, H.; Matsui, Y.; Yotsuya, M.; Matsumoto, F.; Nishio,
(293) Inoue, S.; Todoroki, S.; Suehara, S.; Konishi, T.; Chu, S. Z.; K. Chem. Lett. 2004, 33, 584.
Wada, K.; Kikkojin, T.; Isogai, M.; Katsuta, Y.; Sakamoto, T.; (328) Liu, N. W.; Datta, A.; Liu, C. Y.; Wang, Y. L. Appl. Phys. Lett.
Yasumori, A. J. Non-Cryst. Solids 2006, 352, 632. 2003, 82, 1281.
(294) Musselman, K. P.; Mulholland, G. J.; Robinson, A. P.; Schmidt- (329) Chen, B.; Lu, K.; Tian, Z. Electrochim. Acta 2010, 56, 435.
Mende, L.; MacManus-Driscoll, J. L. Adv. Mater. 2008, 20, 4470. (330) Chen, B.; Lu, K.; Tian, Z. Langmuir 2011, 27, 800.
(295) Foong, T. R. B.; Sellinger, A.; Hu, X. ACS Nano 2008, 2, 2250. (331) Shingubara, S.; Murakami, Y.; Morimoto, K.; Takahagi, T. Surf.
(296) Schierhorn, M.; Boettcher, S. W.; Kraemer, S.; Stucky, G. D.; Sci. 2003, 532−535, 317.
Moskovits, M. Nano Lett. 2009, 9, 3262. (332) Nasir, M. E.; Allsopp, D. W. E.; Bowen, C. R.; Hubbard, G.;
(297) Hill, J. J.; Haller, K.; Ziegler, K. J. J. Electrochem. Soc. 2011, 158, Parsons, K. P. Nanotechnology 2010, 21, 105303.
E1. (333) Xia, Y.; Whitesides, G. M. Annu. Rev. Mater. Sci. 1998, 28, 153.
(298) Chu, S.-Z.; Wada, K.; Inoue, S.; Todoroki, S.-i. Chem. Mater. (334) Guo, L. J. Adv. Mater. 2007, 19, 495.
2002, 14, 4595. (335) Asoh, H.; Nishio, K.; Nakao, M.; Tamamura, T.; Masuda, H. J.
(299) Masuda, H.; Yasui, K.; Sakamoto, Y.; Nakao, M.; Tamamura, Electrochem. Soc. 2001, 148, B152.
T.; Nishio, K. Jpn. J. Appl. Phys. 2001, 40, L1267. (336) Liu, Y.; Goebl, J.; Yin, Y. Chem. Soc. Rev. 2013, 42, 2610.
(300) Kimura, Y.; Shiraki, H.; Ishibashi, K.-i.; Ishii, H.; Itaya, K.; (337) Possin, G. E. Rev. Sci. Instrum. 1970, 41, 772.
Niwanoa, M. J. Electrochem. Soc. 2006, 153, C296. (338) Martin, C. R. Science 1994, 266, 1961.
(301) Holubowitch, N.; Nagle, L. C.; Rohan, J. F. Solid State Ionics (339) Martin, C. R. Adv. Mater. 1991, 3, 457.
2012, 216, 110. (340) Martin, C. R. Chem. Mater. 1996, 8, 1739.
(302) Shimizu, K.; Habazaki, H.; Skeldon, P.; Thompson, G. E.; (341) Penner, R. M.; Martin, C. R. Anal. Chem. 1987, 59, 2625.
Wood, G. C. J. Surf. Finish. Soc. Jpn. 1999, 50, 2. (342) Hurst, S. J.; Payne, E. K.; Qin, L.; Mirkin, C. A. Angew. Chem.,
(303) Skeldon, P.; Shimizu, K.; Thompson, G. E.; Wood, G. C. Int. Ed. 2006, 45, 2672.
Philos. Mag. B 1990, 61, 927. (343) Kovtyukhova, N. I.; Mallouk, T. E. Chem.Eur. J. 2002, 8,
(304) Habazaki, H.; Skeldon, P.; Shimizu, K.; Thompson, G. E.; 4355.
Wood, G. C. Corros. Sci. 1995, 37, 1497. (344) Nicewarner-Peña, S. R.; Freeman, R. G.; Reiss, B. D.; He, L.;
(305) Mozalev, A.; Sakairi, M.; Saeki, I.; Takahashi, H. Electrochim. Peña, D. J.; Walton, I. D.; Cromer, R.; Keating, C. D.; Nata, M. J.
Acta 2003, 48, 3155. Science 2001, 294, 137.
(306) Tatarenko, N. I.; Mozalev, A. M. Solid-State Electron. 2001, 45, (345) Choi, J.; Sauer, G.; Nielsch, K.; Wehrspohn, R. B.; Gösele, U.
1009. Chem. Mater. 2003, 15, 776.
BM dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

(346) Su, Y.-K.; Qin, D.-H.; Zhang, H.-L.; Li, H.; Li, H.-L. Chem. (379) Nishizawa, M.; Menon, V. P.; Martin, C. R. Science 1995, 268,
Phys. Lett. 2004, 388, 406. 700.
(347) Nielsch, K.; Müller, F.; Li, A. P.; Gösele, U. Adv. Mater. 2000, (380) Jirage, K. B.; Hulteen, J. C.; Martin, C. R. Science 1997, 278,
12, 582. 655.
(348) de Menten de Horne, F.; Piraux, L.; Michottea, S. Appl. Phys. (381) Kohli, P.; Wharton, J. E.; Braide, O.; Martin, C. R. J. Nanosci.
Lett. 2005, 86, 152510. Nanotechnol. 2004, 4, 605.
(349) Wang, J.-G.; Tian, M.-L.; Kumar, N.; Mallouk, T. E. Nano Lett. (382) Jirage, K. B.; Hulteen, J. C.; Martin, C. R. Anal. Chem. 1999,
2005, 5, 1247. 71, 4913.
(350) Chaure, N. B.; Stamenov, P.; Rhen, F. M. F.; Coey, J. M. D. J. (383) Martin, C. R.; Nishizawa, M.; Jirage, K.; Kang, M. J. Phys.
Magn. Magn. Mater. 2005, 290−291, 1210. Chem. B 2001, 105, 1925.
(351) Yasui, K.; Morikawa, T.; Nishio, K.; Masuda, H. Jpn. J. Appl. (384) Martin, C. R.; Nishizawa, M.; Jirage, K.; Kang, M.; Lee, S. B.
Phys. 2005, 44, L469. Adv. Mater. 2001, 13, 1351.
(352) Xu, X.; Xu, Y. Mater. Lett. 2006, 60, 2069. (385) Lee, S. B.; Martin, C. R. Chem. Mater. 2001, 13, 3236.
(353) Zhang, Y.; Li, G.; Wu, Y.; Zhang, B.; Song, W.; Zhang, L. Adv. (386) Lee, S. B.; Martin, C. R. J. Am. Chem. Soc. 2002, 124, 11850.
Mater. 2002, 14, 1227. (387) Siwy, Z.; Heins, E.; Harrell, C. C.; Kohli, P.; Martin, C. R. J.
(354) Tok, J. B.-H.; Chuang, F. Y. S.; Kao, M. C.; Rose, K. A.; Pannu, Am. Chem. Soc. 2004, 126, 10850.
S. S.; Sha, M. Y.; Chakarova, G.; Penn, S. G.; Dougherty, G. M. Angew. (388) Yu, S.; Lee, S. B.; Kang, M.; Martin, C. R. Nano Lett. 2001, 1,
Chem., Int. Ed. 2006, 45, 6900. 495.
(355) Walton, I. D.; Norton, S. M.; Balasingham, A.; He, L.; (389) Wirtz, M.; Yu, S.; Martin, C. R. Analyst 2002, 127, 871.
Dominador, F.; Oviso, J.; Gupta, D.; Raju, P. A.; Natan, M. J.; (390) Kobayashi, Y.; Martin, C. R. Anal. Chem. 1999, 71, 3665.
Freeman, R. G. Anal. Chem. 2002, 74, 2240. (391) Wirtz, M.; Parker, M.; Kobayashi, Y.; Martin, C. R. Chem. Rec.
(356) Qin, L.; Park, S.; Huang, L.; Mirkin, C. A. Science 2005, 309, 2002, 2, 259.
113. (392) Steinle, E. D.; Mitchell, D. T.; Wirtz, M.; Lee, S. B.; Young, V.
(357) Chen, X.; Yeganeh, S.; Qin, L.; Li, S.; Xue, C.; Braunschweig, Y.; Martin, C. R. Anal. Chem. 2002, 74, 2416.
A. B.; Schartz, G. C.; Ratner, M. A.; Mirkin, C. A. Nano Lett. 2009, 9, (393) Kohli, P.; Wirtz, M.; Martin, C. R. Electroanalysis 2004, 16, 9.
3974. (394) Yu, Y.; Kant, K.; Shapter, J. G.; Addai-Mensah, J.; Losic, D.
(358) Qin, L.; Banholzer, M. J.; Millstone, J. E.; Mirkin, C. A. Nano Microporous Mesoporous Mater. 2012, 153, 131.
(395) Volpe, M.; Inguanta, R.; Piazza, S.; Sunseri, C. Surf. Coat.
Lett. 2007, 7, 3849.
Technol. 2006, 200, 5800.
(359) Banholzer, M. J.; Qin, L.; Millstone, J. E.; Osberg, K. D.;
(396) Inguanta, R.; Amodeo, M.; D’Agostino, F.; Volpe, M.; Piazza,
Mirkin, C. A. Nat. Protoc. 2009, 4, 838.
S.; Sunseri, C. J. Electrochem. Soc. 2007, 154, D188.
(360) Park, S.; Lim, J.-H.; Chung, S.-W.; Mirkin, C. A. Science 2004,
(397) Wu, J. P.; Brown, I. W. M.; Bowden, M. E.; Kemmitt, T. Solid
303, 348.
State Sci. 2010, 12, 1912.
(361) Ciszek, J. W.; Huang, L.; Wang, Y.; Mirkin, C. A. Small 2008,
(398) Wang, W.; Li, N.; Li, X.; Geng, W.; Qiu, S. Mater. Res. Bull.
4, 206.
2006, 41, 1417.
(362) Yahalom, J.; Zadok, O. J. Mater. Sci. 1987, 22, 499.
(399) Li, N.; Li, X.; Yin, X.; Wang, W.; Qiu, S. Solid State Commun.
(363) Cohen-Hyams, T.; Plitzko, J. M.; Hetherington, C. J. D.;
2004, 132, 841.
Hutchison, J. L.; Yahalom, J.; Kaplan, W. D. J. Mater. Sci. 2004, 39, (400) Chu, S. Z.; Kawamura, H.; Mori, M. J. Electrochem. Soc. 2008,
5701. 155, D414.
(364) Uhlemann, M.; Gebert, A.; Herrich, M.; Krause, A.; Cziraki, A.; (401) Azizi, A.; Mohammadi, M.; Sadrnezhaad, S. K. Mater. Lett.
Schultz, L. Electrochim. Acta 2003, 48, 3005. 2011, 65, 289.
(365) Marsza, M.; Jaworski, J.; Michalik, A.; Prokop, J.; Stachura, Z.; (402) Yuan, X.; Du, C.; Sun, G.; Pan, N. Appl. Surf. Sci. 2007, 253,
Voznyi, V.; Bolling, O.; Sulkio-Cleff, B. J. Magn. Magn. Mater. 2001, 4546.
226−230, 1735. (403) Nagaura, T.; Takeuchi, F.; Yamauchi, Y.; Wada, K.; Inoue, S.
(366) Urbaniak, M.; Luciński, T.; Stobiecki, F. J. Magn. Magn. Mater. Electrochem. Commun. 2008, 10, 681.
1998, 190, 187. (404) Lakshmi, B. B.; Dorhout, P. K.; Martin, C. R. Chem. Mater.
(367) Piraux, L.; George, J. M.; Despres, J. F.; Leroy, C.; Ferain, E.; 1997, 9, 857.
Legras, R.; Ounadjela, K.; Fert, A. Appl. Phys. Lett. 1994, 65, 2484. (405) Lakshmi, B. B.; Patrissi, C. J.; Martin, C. R. Chem. Mater. 1997,
(368) Blondel, A.; Meier, J. P.; Doudin, B.; Ansermet, J.-P. Appl. Phys. 9, 2544.
Lett. 1994, 65, 3019. (406) Hulteen, J. C.; Martin, C. R. J. Mater. Chem. 1997, 7, 1075.
(369) Liu, K.; Nagodawithana, K.; Searson, P. C.; Chien, C. L. Phys. (407) Foong, T. R. B.; Shen, Y.; Hu, X.; Sellinger, A. Adv. Funct.
Rev. B 1995, 51, 7381. Mater. 2010, 20, 1390.
(370) Tourillon, G.; Pontonnier, L.; Levy, J. P.; Langlais, V. (408) Kang, T.-S.; Smith, A. P.; Taylor, B. E.; Durstock, M. F. Nano
Electrochem. Solid-State Lett. 2000, 3, 20. Lett. 2009, 9, 601.
(371) Guo, Y.-G.; Wan, J.-J.; Zhu, C.-F.; Yang, D.-L.; Chen, D.-M.; (409) Wang, G. X.; Park, J. S.; Park, M. S.; Gou, X. L. Sens. Actuators,
Bai, C.-L. Chem. Mater. 2003, 15, 664. B 2008, 131, 313.
(372) Chen, M.; Searson, P. C.; Chien, C. L. J. Appl. Phys. 2003, 93, (410) Ö ztürk, S.; Kılınç, N.; TaşAltin, N.; Ö ztürk, Z. Z. Thin Solid
8253. Films 2011, 520, 932.
(373) Dubois, S.; Marchal, C.; Beuken, J. M.; Piraux, L.; Duvail, J. L.; (411) Ji, G.; Tang, S.; Xu, B.; Gu, B.; Du, Y. Chem. Phys. Lett. 2003,
Fert, A.; George, J. M.; Maurice, J. L. Appl. Phys. Lett. 1999, 70, 396. 379, 484.
(374) Liu, L.; Lee, W.; Scholz, R.; Pippel, E.; Gösele, U. Angew. (412) Wu, Z.; Niu, P.; Yang, B.; Yu, R. Appl. Phys. A: Mater. Sci.
Chem., Int. Ed. 2008, 47, 7004. Process. 2011, 105, 177.
(375) Lee, W.; Scholz, R.; Nielsch, K.; Gösele, U. Angew. Chem., Int. (413) Xu, X.; Qian, T.; Zhang, G.; Zhang, T.; Li, G.; Wang, W.; Li, X.
Ed. 2005, 44, 6050. Chem. Lett. 2007, 36, 112.
(376) Yuan, X. Y.; Wu, G. S.; Xie, T.; Geng, B. Y.; Lin, Y.; Meng, G. (414) Feng, M.; Wang, W.; Zhou, Y.; Jia, D. J. Sol-Gel Sci. Technol.
W.; Zhanga, L. D. Solid State Sci. 2004, 6, 735. 2009, 52, 120.
(377) Yuan, X. Y.; Wu, G. S.; Xie, T.; Lin, Y.; Zhang, L. D. (415) Min, H.-S.; Lee, J.-K. Ferroelectrics 2006, 336, 231.
Nanotechnology 2004, 15, 59. (416) Zhang, G.; Lu, X.; Zhang, T.; Qu, J.; Wang, W.; Li, X.; Yu, S.
(378) Menon, V. P.; Martin, C. R. Anal. Chem. 1995, 67, 1920. Nanotechnology 2006, 17, 4252.
BN dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

(417) Lai, S. H.; Hsu, Y. C.; Lan, M. D. Solid State Commun. 2008, (453) Swan, E. E. L.; Popat, K. C.; Desai, T. A. Biomaterials 2005, 26,
148, 452. 1969.
(418) Wu, G. S.; Lin, Y.; Yuan, X. Y.; Xie, T.; Cheng, B. C.; Zhang, L. (454) Li, P.-F.; Xie, R.; Jiang, J.-C.; Meng, T.; Yang, M.; Ju, X.-J.;
D. Nanotechnology 2004, 15, 568. Yang, L.; Chu, L.-Y. J. Membr. Sci. 2009, 337, 310.
(419) Lei, Y.; Zhang, L. D.; Meng, G. W.; Li, G. H.; Zhang, X. Y.; (455) Sun, L.; Dai, J.; Baker, G. L.; Bruening, M. L. Chem. Mater.
Liang, C. H.; Chen, W.; Wang, S. X. Appl. Phys. Lett. 2001, 78, 1125. 2006, 18, 4033.
(420) Wu, G. S.; Zhuang, Y. L.; Lin, Z. Q.; Yuan, X. Y.; Xie, T.; (456) Jain, P.; Sun, L.; Dai, J.; Baker, G. L.; Bruening, M. L.
Zhang, L. D. Physica E 2006, 31, 5. Biomacromolecules 2007, 8, 3102.
(421) Zhang, M.; Bando, Y.; Wada, K. J. Mater. Res. 2000, 15, 387. (457) Balachandra, A. M.; Baker, G. L.; Bruening, M. L. J. Membr. Sci.
(422) Limmer, S. J.; Seraji, S.; Forbess, M. J.; Wu, Y.; Chou, T. P.; 2003, 227, 1.
Nguyen, C.; Cao, G. Adv. Mater. 2001, 13, 1269. (458) Sun, L.; Baker, G. L.; Bruening, M. L. Macromolecules 2005, 38,
(423) Limmer, S. J.; Seraji, S.; Wu, Y.; Chou, T. P.; Nguyen, C.; Cao, 2307.
G. Adv. Funct. Mater. 2002, 12, 59. (459) Grajales, S. T.; Dong, X.; Zheng, Y.; Baker, G. L.; Bruening, M.
(424) Miao, Z.; Xu, D.; Ouyang, J.; Guo, G.; Zhao, X.; Tang, Y. Nano L. Chem. Mater. 2010, 22, 4026.
Lett. 2002, 2, 717. (460) Shi, W.; Shen, Y.; Ge, D.; Xue, M.; Cao, H.; Huang, S.; Wang,
(425) Lee, S. B.; Mitchell, D. T.; Trofin, L.; Nevanen, T. K.; J.; Zhang, G.; Zhang, F. J. Membr. Sci. 2008, 325, 801.
Söderlund, H.; Martin, C. R. Science 2002, 296, 2198. (461) Song, C.; Shi, W.; Jiang, H.; Tu, J.; Ge, D. J. Membr. Sci. 2011,
(426) Mitchell, D. T.; Lee, S. B.; Trofin, L.; Li, N.; Nevanen, T. K.; 372, 340.
Söderlund, H.; Martin, C. R. J. Am. Chem. Soc. 2002, 124, 11864. (462) Bruening, M. L.; Dotzauer, D. M.; Jain, P.; Ouyang, L.; Baker,
(427) Son, S. J.; Lee, S. B. J. Am. Chem. Soc. 2006, 128, 15974. G. L. Langmuir 2008, 24, 7663.
(428) Buyukserin, F.; Martin, C. R. Appl. Surf. Sci. 2010, 256, 7700. (463) Decher, G. Science 1997, 277, 1232.
(429) Hillebrenner, H.; Buyukseri, F.; Kang, M.; Mota, M. O.; (464) Jin, W.; Toutianoush, A.; Tieke, B. Langmuir 2003, 19, 2550.
Stewart, J. D.; Martin, C. R. J. Am. Chem. Soc. 2006, 128, 4236. (465) Toutianoush, A.; Tieke, B. Mater. Sci. Eng., C 2002, 22, 135.
(430) Chen, C.-C.; Liu, Y.-C.; Wu, C.-H.; Yeh, C.-C.; Su, M.-T.; Wu, (466) Peyratout, C. S.; Dähne, L. Angew. Chem., Int. Ed. 2004, 43,
Y.-C. Adv. Mater. 2005, 17, 404. 3762.
(431) Yamacuchi, A.; Uejo, F.; Yoda, T.; Uchida, T.; Tanamura, Y.; (467) Balachandra, A. M.; Dai, J.; Bruening, M. L. Macromolecules
Yamashita, T.; Teramae, N. Nat. Mater. 2004, 3, 337. 2002, 35, 3171.
(432) Platschek, B.; Petkov, N.; Bein, T. Angew. Chem., Int. Ed. 2006, (468) Liu, X.; Bruening, M. L. Chem. Mater. 2004, 16, 351.
45, 1134. (469) Hong, S. U.; Ouyang, L.; Bruening, M. L. J. Membr. Sci. 2009,
(433) Platschek, B.; Petkov, N.; Himsl, D.; Zimdars, S.; Li, Z.; Köhn, 327, 2.
R.; Bein, T. J. Am. Chem. Soc. 2008, 130, 17362. (470) Ouyang, L.; Malaisamy, R.; Bruening, M. L. J. Membr. Sci.
(434) Wu, Y.; Cheng, G.; Katsov, K.; Sides, S. W.; Wang, J.; Tang, J.; 2008, 310, 76.
Fredrickson, G. H.; Moskovits, M.; Stucky, G. D. Nat. Mater. 2004, 3, (471) Dai, J.; Baker, G. L.; Brening, M. L. Anal. Chem. 2006, 78, 135.
816. (472) Liang, Z.; Susha, A. S.; Yu, A.; Caruso, F. Adv. Mater. 2003, 15,
(435) Chang, C.-S.; Suen, S.-Y. J. Membr. Sci. 2006, 275, 70. 1849.
(436) Cheow, P.-S.; Liu, L.; Toh, C.-S. Surf. Interface Anal. 2007, 39, (473) Lee, D.; Nolte, A. J.; Kunz, A. L.; Rubner, M. F.; Cohen, R. E. J.
601. Am. Chem. Soc. 2006, 128, 8521.
(437) Ö berg, K.; Persson, P.; Shchukarev, A.; Eliassona, B. Thin Solid (474) Lee, D.; Cohen, R. E.; Rubner, M. F. Langmuir 2007, 23, 123.
Films 2001, 397, 102. (475) Ai, S.; Lu, G.; He, Q.; Li, J. J. Am. Chem. Soc. 2003, 125, 11140.
(438) Liakos, I. L.; Newman, R. C.; McAlpine, E.; Alexander, M. R. (476) Feng, C.-L.; Zhong, X.; Steinhart, M.; Caminade, A.-M.;
Surf. Interface Anal. 2004, 36, 37. Majoral, J.-P.; Knoll, W. Adv. Mater. 2007, 19, 1993.
(439) Chen, Y.-F.; Hu, Y.-H.; Chou, Y.-I.; Lai, S.-M.; Wang, C.-C. (477) Tian, Y.; He, Q.; Tao, C.; Li, J. Langmuir 2006, 22, 360.
Sens. Actuators, B 2010, 145, 575. (478) Alem, H.; Blondeau, F.; Glinel, K.; Demoustier-Champagne, S.;
(440) Yildirim, O.; Gang, T.; Kinge, S.; Reinhoudt, D. N.; Blank, D. Jonas, A. M. Macromolecules 2007, 40, 3366.
H. A.; Van der Wiel, W. G.; Rijnders, G.; Huskens, J. Int. J. Mol. Sci. (479) Cho, Y.; Lee, W.; Jhon, Y. K.; Genzer, J.; Char, K. Small 2010,
2010, 11, 1162. 6, 2683.
(441) Jani, A. M. M.; Anglin, E. J.; McInnes, S. J. P.; Losic, D.; (480) Hou, S.; Harrell, C. C.; Trofin, L.; Kohli, P.; Martin, C. R. J.
Shapter, J. G.; Voelcker, N. H. Chem. Commun. 2009, 3062. Am. Chem. Soc. 2004, 126, 5674.
(442) Jani, A. M. M.; Kempson, I. M.; Losic, D.; Voelcker, N. H. (481) Quinn, J. F.; Johnston, A. P. R.; Such, G. K.; Zelikin, A. N.;
Angew. Chem., Int. Ed. 2010, 49, 7933. Caruso, F. Chem. Soc. Rev. 2007, 36, 707.
(443) Ko, H.; Tsukruk, V. V. Small 2008, 4, 1980. (482) Kongsuphol, P.; Fang, K. B.; Ding, Z. Sens. Actuators, B 2013,
(444) Dotzauer, D. M.; Dai, J.; Sun, L.; Bruening, M. L. Nano Lett. 185, 530.
2006, 6, 2268. (483) Hirano-Iwata, A.; Taira, T.; Oshima, A.; Kimura, Y.; Niwano,
(445) He, Q.; Cui, Y.; Ai, S.; Tian, Y.; Li, J. Curr. Opin. Colloid M. Appl. Phys. Lett. 2010, 96, 213706.
Interface Sci. 2009, 14, 115. (484) Bally, M.; Bailey, K.; Sugihara, K.; Grieshaber, D.; Vörös, J.;
(446) Lahav, M.; Sehayek, T.; Vaskevich, A.; Rubinstein, I. Angew. Städler, a. B. Small 2010, 6, 2481.
Chem., Int. Ed. 2003, 42, 5576. (485) Hirano-Iwata, A.; Niwano, M.; Sugawara, M. Trends Anal.
(447) Hobler, C.; Bakowsky, U.; Keusgen, M. Phys. Status Solidi A Chem. 2008, 27, 512.
2010, 207, 872. (486) Hennesthal, C.; Steinem, C. J. Am. Chem. Soc. 2000, 122, 8085.
(448) Thormann, A.; Teuscher, N.; Pfannmçller, M.; Rothe, U.; (487) Naumann, R.; Jonczyk, A.; Kopp, R.; van Esch, J.; Ringsdorf,
Heilmann, A. Small 2007, 3, 1032. H.; Knoll, W.; Griiber, P. Angew. Chem., Int. Ed. 1995, 34, 2056.
(449) Lu, Z.; Ruan, W.; Yang, J.; Xu, W.; Zhao, C.; Zhao, B. J. Raman (488) Cremer, P. S.; Boxer, S. G. J. Phys. Chem. B 1999, 103, 2554.
Spectrosc. 2008, 40, 112. (489) Rädler, J.; Strey, H.; Sackmann, E. Langmuir 1995, 11, 4539.
(450) Ji, N.; Ruan, W.; Wang, C.; Lu, Z.; Zhao, B. Langmuir 2009, 25, (490) Sackmann, E. Science 1995, 271, 43.
11869. (491) Sackmann, E.; Tanaka, M. Trends Biotechnol. 2000, 18, 58.
(451) Sehayek, T.; Lahav, M.; Popovitz-Biro, R.; Vaskevich, A.; (492) Heyse, S.; Ernst, O. P.; Dienes, Z.; Hofmann, K. P.; Vogel, A.
Rubinsein, I. Chem. Mater. 2005, 17, 3743. H. Biochemistry 1998, 37, 507.
(452) Tanvir, S.; Pantigny, J.; Boulnois, P.; Pulvin, S. J. Membr. Sci. (493) Mayer, M.; Kriebel, J. K.; Tosteson, M. T.; Whitesides, G. M.
2009, 329, 85. Biophys. J. 2003, 85, 2684.
BO dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

(494) Simon, A.; Girard-Egrot, A.; Sauter, F.; Pudda, C.; D’Hahan, N. (530) Mei, X.; Blumin, M.; Kim, D.; Wu, Z.; Ruda, H. E. J. Cryst.
P.; Blum, L.; Chatelain, F.; Fuchs, A. J. Colloid Interface Sci. 2007, 308, Growth 2003, 251, 253.
337. (531) Jung, M.; Lee, H. S.; Park, H. L.; Mho, S.-i. Curr. Appl. Phys.
(495) Hennesthal, C.; Drexler, J.; Steinem, C. ChemPhysChem 2002, 2006, 6S1, e187.
10, 885. (532) Mei, X.; Blumin, M.; Sun, M.; Kim, D.; Wu, Z. H.; Ruda, H. E.;
(496) Römer, W.; Steinem, C. Biophys. J. 2004, 86, 955. Guo, Q. X. Appl. Phys. Lett. 2003, 82, 967.
(497) Schmitt, E. K.; Vrouenraets, M.; Steinem, C. Biophys. J. 2006, (533) Chen, Z.; Lei, Y.; Chew, H. G.; Teo, L. W.; Choi, W. K.; Chim,
91, 2163. W. K. J. Cryst. Growth 2004, 268, 560.
(498) Schmitt, E. K.; Nurnabi, M.; Bushby, R. J.; Steinem, C. Soft (534) Xu, W. L.; Zheng, M. J.; Ding, G. Q.; Shen, W. Z. Chem. Phys.
Matter 2008, 4, 250. Lett. 2005, 411, 37.
(499) Schmitt, E. K.; Weichbrodt, C.; Steinem, C. Soft Matter 2009, (535) Guo, Q.; Mei, X.; Ruda, H.; Tanaka, T.; Nishio, M.; Ogawa, H.
5, 3347. Jpn. J. Appl. Phys. 2003, 42, L508.
(500) Lazzara, T. D.; Carnarius, C.; Kocun, M.; Janshoff, A.; Steinem, (536) Masuda, H.; Yasui, K.; Nishio, K. Adv. Mater. 2000, 12, 1031.
C. ACS Nano 2011, 5, 6935. (537) Liu, K.; Nogués, J.; Leighton, C.; Masuda, H.; Nishio, K.;
(501) Hotta, K.; Yamaguchi, A.; Teramae, N. ACS Nano 2013, 6, Roshchin, I. V.; Schuller, I. K. Appl. Phys. Lett. 2002, 81, 4434.
1541. (538) Nam, W.; Seo, H.; Park, S. C.; Bae, C. H.; Nam, S. H.; Park, S.
(502) Smirnov, A. I.; Poluektov, O. G. J. Am. Chem. Soc. 2003, 125, M.; Ha, J. S. Jpn. J. Appl. Phys. 2004, 43, 7793.
8434. (539) Kossyrev, P. A.; Yin, A.; Cloutier, S. G.; Cardimona, D. A.;
(503) Chekmenev, E. Y.; Gor’kov, P. L.; Cross, T. A.; Alaouie, A. M.; Huang, D.; Alsing, P. M.; Xu, J. M. Nano Lett. 2005, 5, 1978.
Smirnov, A. I. Biophys. J. 2006, 91, 3076. (540) Lei, Y.; Chim, W.-K. J. Am. Chem. Soc. 2005, 127, 1487.
(504) Li, R.-Q.; Marek, A.; Smirnov, A. I.; Grebel, H. J. Chem. Phys. (541) Gao, X.; Liu, L.; Birajdar, B.; Ziese, M.; Lee, W.; Alexe, M.;
2008, 129, 095102. Hesse, D. Adv. Funct. Mater. 2009, 19, 3450.
(505) Demé, B.; Marchal, D. Eur. Biophys. J. 2005, 34, 170. (542) Lee, W.; Han, H.; Lotnyk, A.; Schubert, M. A.; Senz, S.; Alexe,
(506) Parthasarathy, R. V.; Martin, C. R. Nature 1994, 369, 298. M.; Hesse, D.; Baik, S.; Gösele, U. Nat. Nanotechnol. 2008, 3, 402.
(507) Cai, Z.; Lei, J.; Liang, W.; Menon, V.; Martin, C. R. Chem. (543) Rodriguez, B. J.; Gao, X. S.; Liu, L. F.; Lee, W.; Naumov, I. I.;
Mater. 1991, 3, 960. Bratkovsky, A. M.; Hesse, D.; Alexe, M. Nano Lett. 2009, 9, 1127.
(508) Parthasarathy, R. V.; Martin, C. R. Chem. Mater. 1994, 6, 1627. (544) Kim, Y.; Han, H.; Lee, W.; Baik, S.; Hesse, D.; Alexe, M. Nano
(509) Martin, C. R. Acc. Chem. Res. 1995, 28, 61. Lett. 2010, 10, 1266.
(510) Parthasarathy, R. V.; Phani, K. L. N.; Martin, C. R. Adv. Mater. (545) Han, H.; Park, Y. J.; Baik, S.; Lee, W.; Alexe, M.; Hesse, D.;
1995, 7, 896. Gösele, U. J. Appl. Phys. 2010, 108, 044102.
(511) Steinhart, M.; Wendorff, J. H.; Greiner, A.; Wehrspohn, R. B.; (546) Han, H.; Kim, Y.; Alexe, M.; Hesse, D.; Lee, W. Adv. Mater.
Nielsch, K.; Schilling, J.; Choi, J.; Gösele, U. Science 2002, 296, 1997. 2011, 23, 4599.
(512) de Gennes, P. G. Rev. Mod. Phys. 1985, 57, 827. (547) Cheng, G.; Moskovits, M. Adv. Mater. 2002, 14, 1567.
(513) Ausserré, D.; Picard, A. M.; Léger, L. Phys. Rev. Lett. 1986, 57, (548) Liang, J.; Chik, H.; Yin, A.; Xu, J. J. Appl. Phys. 2002, 91, 2544.
2671. (549) Liang, J.; Hong, S.-K.; Kouklin, N.; Beresford, B.; Xu, J. M.
(514) Heslot, F.; Cazabat, A. M.; Levinson, P. Phys. Rev. Lett. 1989, Appl. Phys. Lett. 2003, 83, 1752.
62, 1286. (550) Shingubara, S.; Okino, O.; Murakami, Y.; Sakaue, H.; Takahagi,
(515) Steinhart, M.; Wendorff, J. H.; Wehrspohn, R. B. T. J. Vac. Sci. Technol., B 2001, 19, 1901.
ChemPhysChem 2003, 4, 1171. (551) Nakao, M.; Oku, S.; Tamamura, T.; Yasui, K.; Masuda, H. Jpn.
(516) Steinhart, M.; Wehrspohn, R. B.; Gösele, U.; Wendorff, J. H. J. Appl. Phys. 1999, 38, 1052.
Angew. Chem., Int. Ed. 2004, 43, 1334. (552) Guo, Q.; Takaka, T.; Nishio, M.; Ogawa, H.; Mei, X.; Ruda, H.
(517) Lee, W.; Jin, M.-K.; Yoo, W.-C.; Lee, J.-L. Langmuir 2004, 20, Jpn. J. Appl. Phys. 2002, 41, L118.
7665. (553) Kouklin, N.; Chik, H.; Liang, J.; Tzolov, M.; Xu, J. M.; Heroux,
(518) Steinhart, M.; Senz, S.; Wehrsphon, R. B.; Gösele, U.; J. B.; Wang, W. I. J. Phys. D: Appl. Phys. 2003, 36, 2634.
Wendorff, J. H. Macromolecules 2003, 36, 3646. (554) Liang, J.; Luo, H.; Beresford, R.; Xu, J. Appl. Phys. Lett. 2004,
(519) Steinhart, M.; Zimmermann, S.; Göring, P.; Schaper, A. K.; 85, 5974.
Gösele, U.; Weder, C.; Wndorff, J. H. Nano Lett. 2005, 5, 429. (555) Kanamori, Y.; Hane, K.; Sai, H.; Yugami, H. Appl. Phys. Lett.
(520) Steinhart, M.; Murano, S.; Shaper, A. K.; Ogawa, T.; Tsuji, M.; 2001, 78, 142.
Gösele, U.; Weder, C.; Wendorff, J. H. Adv. Funct. Mater. 2005, 15, (556) Tian, L.; Ram, K. B.; Ahmad, I.; Menon, L.; Holtz, M. J. Appl.
1656. Phys. 2005, 97, 026101.
(521) Steinhart, M.; Jia, Z.; Schaper, A. K.; Wehrspohn, R. B.; Gösele, (557) Masuda, H.; Watanabe, M.; Yasui, K.; Tryk, D.; Rao, T.;
U.; Wendorff, J. H. Adv. Mater. 2003, 15, 706. Fujishima, A. Adv. Mater. 2000, 12, 444.
(522) Luo, Y.; Lee, S. K.; Hofmeister, H.; Steinhart, M.; Gösele, U. (558) Masuda, H.; Yasui, K.; Watanabe, M.; Nishio, K.; Nakao, M.;
Nano Lett. 2004, 4, 143. Tamamura, T.; Rao, T. N.; Fujishima, A. Electrochem. Solid-State Lett.
(523) Lei, Y.; Cai, W.; Wilde, G. Prog. Mater. Sci. 2007, 52, 465. 2001, 4, G101.
(524) Sulka, G. D.; Zaraska, L.; Stępniowski, W. J. Anodic Porous (559) Honda, K.; Rao, T. N.; Tryk, D. A.; Fujishima, A.; Watanabe,
Alumina as a Template for Nanofabrication. In Encylopedia of M.; Yasui, K. J. Electrochem. Soc. 2001, 148, A668.
Nanoscience and Nanotechnology, 2nd ed.; Nalwa, H. S., Ed.; American (560) Honda, K.; Rao, T. N.; Tryk, D. A.; Fujishima, A.; Watanabe,
Scientific Publishers: Califonia, 2011; Vol. 11, pp 261−349. M.; Yasui, K.; Masuda, H. J. Electrochem. Soc. 2000, 147, 659.
(525) Meng, G.; Yanagida, T.; Nagashima, K.; Yanagishita, T.; Kanai, (561) Nakao, M.; Oku, S.; Tanaka, H.; Shibata, Y.; Yokoo, A.;
M.; Oka, K.; Klamchuen, A.; Rohong, S.; Horprathum, M.; Xu, B.; Tamamura, T.; Masuda, H. Opt. Quantum Electron. 2002, 34, 183.
Zhuge, F.; He, Y.; Masuda, H.; Kawai, T. RSC Adv. 2012, 2, 10618. (562) Wang, Y. D.; Chua, S. J.; Sander, M. S.; Chen, P.; Tripathy, S.;
(526) Mei, X.; Kim, D.; Ruda, H. E.; Guo, Q. X. Appl. Phys. Lett. Fonstad, C. G. Appl. Phys. Lett. 2004, 85, 816.
2003, 81, 361. (563) Hobbs, K. L.; Larson, P. R.; Lian, G. D.; Keay, J. C.; Johnson,
(527) Lei, Y.; Chim, W.-K. Chem. Mater. 2005, 17, 580. M. B. Nano Lett. 2004, 4, 167.
(528) Lei, Y.; Chim, W. K.; Sun, H. P.; Wilde, G. Appl. Phys. Lett. (564) Lombardi, I.; Hochbaum, A. I.; Yang, P.; Carraro, C.;
2005, 86, 103106. Maboudian, R. Chem. Mater. 2006, 18, 988.
(529) Cloutier, S. G.; Guico, R. S.; Xu, J. M. Appl. Phys. Lett. 2005, (565) Lei, Y.; Yeong, K.-S.; Thong, J. T. L.; Chim, W.-K. Chem.
87, 222104. Mater. 2004, 16, 2757.
BP dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

(566) Wu, Z. H.; Mei, X. Y.; Kim, D.; Blumin, M.; Ruda, H. E. Appl. (601) Shen, X.-P.; Han, M.; Hong, J.-M.; Xue, Z.; Xu, Z. Chem. Vap.
Phys. Lett. 2002, 81, 5177. Deposition 2005, 11, 250.
(567) Chik, H.; Liang, J.; Cloutier, S. G.; Kouklin, N.; Xu, J. M. Appl. (602) Fan, Z.; Razavi, H.; Do, J.-w.; Moriwaki, A.; Ergen, O.; Chueh,
Phys. Lett. 2004, 84, 3376. Y.-L.; Leu, P. W.; Ho, J. C.; Takahashi, T.; Reichertz, L. A.; Neale, S.;
(568) Lee, W.; Alexe, M.; Nielsch, K.; Gösele, U. Chem. Mater. 2005, Yu, K.; Wu, M.; Ager, J. W.; Javey, A. Nat. Mater. 2009, 8, 648.
17, 3325. (603) Fan, Z.; Dutta, D.; Chien, C.-J.; Chen, H.-Y.; Brown, E. C.
(569) Fan, H. J.; Lee, W.; Hauschild, R.; Alexe, M.; Le Rhun, G.; Appl. Phys. Lett. 2006, 89, 213110.
Scholz, R.; Dadgar, A.; Nielsch, K.; Kalt, H.; Krost, A.; Zacharias, M.; (604) Bae, C.; Yoo, H.; Kim, S.; Lee, K.; Kim, J.; Sung, M. M.; Shin,
Gösele, U. Small 2006, 2, 561. H. Chem. Mater. 2008, 20, 756.
(570) Fan, H. J.; Lee, W.; Scholz, R.; Dadgar, A.; Krost, A.; Nielsch, (605) Detavernier, C.; Dendooven, J.; Pulinthanathu Sree, S.;
K.; Zacharias, M. Nanotechnology 2005, 16, 913. Ludwig, K. F.; Martens, J. A. Chem. Soc. Rev. 2011, 40, 5242.
(571) Lee, S. K.; Lee, W.; Alexe, M.; Nielsch, K.; Hesse, D.; Gösele, (606) George, S. M. Chem. Rev. 2009, 110, 111.
U. Appl. Phys. Lett. 2005, 86, 152906. (607) Knez, M.; Nielsch, K.; Niinistö, L. Adv. Mater. 2007, 19, 3425.
(572) Lee, S. K.; Hesse, D.; Alexe, M.; Lee, W.; Nielsch, K.; Gösele, (608) Marichy, C.; Bechelany, M.; Pinna, N. Adv. Mater. 2012, 24,
U. J. Appl. Phys. 2005, 98, 124302. 1017.
(573) Park, S.-J.; Han, H.; Rhu, H.; Baik, S.; Lee, W. J. Mater. Chem. (609) Narayan, R.; Monteiro-Riviere, N. A.; Brigmon, R. L.; Pellin,
C 2013, 1, 5330. M. J.; Elam, J. W. JOM 2009, 61, 12.
(574) Han, H.; Kim, J.; Shin, H. S.; Song, J. Y.; Lee, W. Adv. Mater. (610) Ott, A. W.; Klaus, J. W.; Johnson, J. M.; George, S. M.;
2012, 24, 2284. McCarley, K. C.; Way, J. D. Chem. Mater. 1997, 9, 707.
(575) Kim, J.; Han, H.; Kim, Y. H.; Choi, S.-H.; Kim, J.-C.; Lee, W. (611) Chen, P.; Mitsui, T.; Farmer, D. B.; Golovchenko, J.; Gordon,
ACS Nano 2011, 5, 3222. R. G.; Branton, D. Nano Lett. 2004, 4, 1333.
(576) Kim, J.; Kim, Y. H.; Choi, S.-H.; Lee, W. ACS Nano 2011, 5, (612) Velleman, L.; Triani, G.; Evans, P. J.; Shapter, J. G.; Losic, D.
5242. Microporous Mesoporous Mater. 2009, 126, 87.
(577) Kim, J.; Rhu, H.; Lee, W. J. Mater. Chem. 2011, 21, 15889. (613) Kim, W.-H.; Park, S.-J.; Son, J.-Y.; Kim, H. Nanotechnology
(578) Huang, Z.; Zhang, X.; Reiche, M.; Liu, L.; Lee, W.; Shimizu, T.; 2008, 19, 045302.
Senz, S.; Gösele, U. Nano Lett. 2008, 8, 3046. (614) Chang, Y.-H.; Wang, S.-M.; Liu, C.-M.; Chen, C. J. Electrochem.
(579) Hulteen, J. C.; Martin, C. R. Template synthesis of Soc. 2010, 157, K236.
(615) Yang, C.-J.; Wang, S.-M.; Liang, S.-W.; Chang, Y.-H.; Chen, C.;
nanoparticles in nanoporous membranes. In Nanoparticles and
Shieh, J.-M. Appl. Phys. Lett. 2007, 90, 033104.
Nanostructured Films: Preparation, Characterization and Applications;
(616) Bachmann, J.; Jing, J.; Knez, M.; Barth, S.; Shen, H.; Mathur,
Fendler, J. H., Ed.; Wiley-VCH: New York, 1998; pp 235−262.
S.; Gösele, U.; Nielsch, K. J. Am. Chem. Soc. 2007, 129, 9554.
(580) Shingubara, S. J. Nanopart. Res. 2003, 5, 17.
(617) Bae, C.; Yoon, Y.; Yoo, H.; Han, D.; Cho, J.; Lee, B. H.; Sung,
(581) Kyotani, T.; Tsai, L.-f.; Tomita, A. Chem. Mater. 1996, 8, 2109.
M. M.; Lee, M.; Kim, J.; Shin, H. Chem. Mater. 2009, 21, 2574.
(582) Che, G.; Lakshmi, B. B.; Martin, C. R.; Fisher, E. R. Chem.
(618) Bae, C.; Zierold, R.; Montero Moreno, J. M.; Kim, H.; Shin,
Mater. 1998, 10, 260.
H.; Bachmann, J.; Nielsch, K. J. Mater. Chem. C 2013, 1, 621.
(583) Li, J.; Papadopoulos, C.; Xu, J. M. Appl. Phys. Lett. 1999, 75,
(619) Comstock, D. J.; Christensen, S. T.; Elam, J. W.; Pellin, M. J.;
367. Hersam, M. C. Adv. Funct. Mater. 2010, 20, 3099.
(584) Suh, J. S.; Lee, J. S. Appl. Phys. Lett. 1999, 75, 2047. (620) Gaspard, P.; Hithesh, K. G.; Göran, S.; Wouter van der, W.;
(585) Jeong, S.-H.; Hwang, H.-Y.; Lee, K.-H.; Jeong, Y. Appl. Phys.
Niclas, R. Nanotechnology 2013, 24, 015602.
Lett. 2001, 78, 2052. (621) Gu, D.; Baumgart, H.; Abdel-Fattah, T. M.; Namkoong, G.
(586) Yanagishita, T.; Sasaki, M.; Nishio, K.; Masuda, H. Adv. Mater. ACS Nano 2010, 4, 753.
2004, 16, 429. (622) Marianna, K.; Emma, H.; Viljami, P.; Mikko, R.; Markku, L.
(587) Meng, G.; Jung, Y. J.; Cao, A.; Vajtai, R.; Ajayan, P. M. Proc. Nanotechnology 2010, 21, 035301.
Natl. Acad. Sci. U.S.A. 2005, 102, 7074. (623) Pitzschel, K.; Moreno, J. M. M.; Escrig, J.; Albrecht, O.;
(588) Chen, Q.-L.; Xue, K.-H.; Shen, W.; Tao, F.-F.; Yin, S.-Y.; Xu, Nielsch, K.; Bachmann, J. ACS Nano 2009, 3, 3463.
W. Electrochim. Acta 2004, 49, 4157. (624) Shin, H.; Jeong, D. K.; Lee, J.; Sung, M. M.; Kim, J. Adv. Mater.
(589) Park, S.; Kim, Y.-S.; Kim, W. B.; Jon, S. Nano Lett. 2009, 9, 2004, 16, 1197.
1325. (625) Yoon, J.; Kim, S.; No, K. Mater. Lett. 2012, 87, 124.
(590) Schmidt, V.; Wittemann, J. V.; Gösele, U. Chem. Rev. 2010, (626) Martinson, A. B. F.; Elam, J. W.; Hupp, J. T.; Pellin, M. J. Nano
110, 361. Lett. 2007, 7, 2183.
(591) Schmidt, V.; Senz, S.; Gösele, U. Nano Lett. 2005, 5, 931. (627) Sander, M. S.; Côté, M. J.; Gu, W.; Kile, B. M.; Tripp, C. P.
(592) Shimizu, T.; Xie, T.; Nishikawa, J.; Shingubara, S.; Senz, S.; Adv. Mater. 2004, 16, 2052.
Gösele, U. Adv. Mater. 2007, 19, 917. (628) Bachmann, J.; Zierold, R.; Chong, Y. T.; Hauert, R.; Sturm, C.;
(593) Gorisse, T.; Dupré, L.; Gentile, P.; Martin, M.; Zelsmann, M.; Schmidt-Grund, R.; Rheinländer, B.; Grundmann, M.; Gösele, U.;
Buttard, D. Nanoscale Res. Lett. 2013, 8, 287. Nielsch, K. Angew. Chem., Int. Ed. 2008, 47, 6177.
(594) Cheng, G. S.; Zhang, L. D.; Zhu, Y.; Fei, G. T.; Li, L.; Mo, C. (629) Bae, C.; Yoon, Y.; Yoon, W.-S.; Moon, J.; Kim, J.; Shin, H. ACS
M.; Mao, Y. Q. Appl. Phys. Lett. 1999, 75, 2455. Appl. Mater. Interfaces 2010, 2, 1581.
(595) Zhang, J.; Zhang, L. D.; Wang, X. F.; Liang, C. H.; Peng, X. S.; (630) Chen, X.; Pomerantseva, E.; Banerjee, P.; Gregorczyk, K.;
Wang, Y. W. J. Appl. Phys. 2001, 115, 5714. Ghodssi, R.; Rubloff, G. Chem. Mater. 2012, 24, 1255.
(596) Jung, W.-G.; Jung, S.-H.; Kung, P.; Razeghi, M. Nanotechnology (631) Panda, S. K.; Yoon, Y.; Jung, H. S.; Yoon, W.-S.; Shin, H. J.
2006, 17, 54. Power Sources 2012, 204, 162.
(597) Li, X.; Meng, G.; Xu, Q.; Kong, M.; Zhu, X.; Chu, Z.; Li, A.-P. (632) Banerjee, P.; Perez, I.; Henn-Lecordier, L.; Lee, S. B.; Rubloff,
Nano Lett. 2011, 11, 1704. G. W. Nat. Nanotechnol. 2009, 4, 292.
(598) Li, X.; Meng, G.; Qin, S.; Xu, Q.; Chu, Z.; Zhu, X.; Kong, M.; (633) Du, X.; George, S. M. Sens. Actuators, B 2008, 135, 152.
Li, A.-P. ACS Nano 2012, 6, 831. (634) Moreno i Codinachs, L.; Birkenstock, C.; Garma, T.; Zierold,
(599) Shen, X.-P.; Yuan, A.-H.; Wang, F.; Hong, J.-M.; Xu, Z. Solid R.; Bachmann, J.; Nielsch, K.; Schöning, M. J.; Fontcuberta i Morral,
State Commun. 2005, 133, 19. A. Phys. Status Solidi A 2009, 206, 435.
(600) Shen, X.-P.; Liu, J.-J.; Fan, X.; Jiang, Y.; Hong, J.-M.; Xu, Z. J. (635) Lee, J.; Kim, D. H.; Hong, S.-H.; Jho, J. Y. Sens. Actuators, B
Cryst. Growth 2005, 276, 471. 2011, 160, 1494.
BQ dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

(636) Liu, C.-M.; Chen, C.; Cheng, H.-E. Electrochem. Solid-State Lett.
2011, 14, K33.
(637) Cameron, M. A.; Gartland, I. P.; Smith, J. A.; Diaz, S. F.;
George, S. M. Langmuir 2000, 16, 7435.
(638) Tran, T. H. Y.; Haije, W. G.; Longo, V.; Kessels, W. M. M.;
Schoonman, J. J. Membr. Sci. 2011, 378, 438.
(639) Pellin, M. J.; Stair, P. C.; Xiong, G.; Elam, J. W.; Birrell, J.;
Curtiss, L.; George, S. M.; Han, C. Y.; Iton, L.; Kung, H.; Kung, M.;
Wang, H. H. Catal. Lett. 2005, 102, 127.
(640) Stair, P. C.; Marshall, C.; Xiong, G.; Feng, H.; Pellin, M. J.;
Elam, J. W.; Curtiss, L.; Iton, L.; Kung, H.; Kung, M.; Wang, H. H.
Top. Catal. 2006, 39, 181.
(641) Kemell, M.; Pore, V.; Tupala, J.; Ritala, M.; Leskelä, M. Chem.
Mater. 2007, 19, 1816.
(642) Tan, L. K.; Kumar, M. K.; An, W. W.; Gao, H. ACS Appl.
Mater. Interfaces 2010, 2, 498.
(643) Lee, J. H.; Wu, J. H.; Liu, H. L.; Cho, J. U.; Cho, M. K.; An, B.
H.; Min, J. H.; Noh, S. J.; Kim, Y. K. Angew. Chem., Int. Ed. 2007, 46,
3663.
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Porous Anodic Aluminum Oxide: Anodization and Templated Synthesis of Functional Nanostructures

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Porous Anodic Aluminum Oxide: Anodization and Templated Synthesis of Functional Nanostructures

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Review

Porous Anodic Aluminum Oxide: Anodization and Templated

aluminum, new oxide forms above and below the marker

C dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

D dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

Figure 5. Cross-sectional transmission electron microscopy (TEM)

= (ψi /rq)(ln je,B − ln γ1) + (2.3ψiγ2/rq) log ρe (36)

Figure 9. Band diagram showing the avalanche multiplication of

je = je, x = 0 exp[αtox ]=je, x = 0 exp[αβU ] (39)

dU ⎛ 1 ⎞⎛ E ⎞⎛ M M2 ⎞ Further, by ﬁtting eq 44 on the experimental potential

at the rate (ζp) of 1.29 nm V−1 with respect to the anodizing

They pointed out that the electrolyte concentration does not

H 2SO4 −AAO > H 2C2O4 −AAO > H3PO4 −AAO

Figure 16. Distribution of the potential drop and electric ﬁeld, E

6. GROWTH OF POROUS ANODIC ALUMINUM OXIDE

Figure 20. A schematic illustration of volume expansion during

For three major pore-forming acid electrolytes (i.e., H2SO4,

during the very initial stage of pore formation in 0.4 M

S dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

(i.e., potential vs time) was characterized by three well-deﬁned

Figure 25. Dependence of the oxide formation eﬃciency (ηj) on

V−1 for aluminum anodizing in 1.0 M H2SO4, they then could

The model also predicted a linear dependence of interpore

AB dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

evolution of a large amount of heat:4,18,79,89,94,97,238,239 UB = 27,

agent for lowering the freezing point of the electrolyte down to

popularly been employed in the aluminum industry to produce

dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

Kohli et al.381 noted that the above electroless deposition

a rather complex evolution of mesochannels with the geometric

AU dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

mixture solutions containing Pd(OAc)2 and poly(D,L-lactide)

also been used either as etching masks in dry etching processes

BB dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

emitters,585 electrodes for supercapacitors,588 and platforms for

nature, avoiding CVD-like ﬁlm growth. By virtue of such a self-

have been independently reported by Comstock et al.619 and

10. CLOSING REMARKS AND OUTLOOK

Biographies the former director of Max-Planck-Institut für Mikrostruktur-

γ the ratio j2/j1 EM elastic modulus of metal strip

BH dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

OWL on-wire lithography S spreading parameter

BI dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

BJ dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

BK dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

BL dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

BM dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

BN dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

BO dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

BP dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

BQ dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

BR dx.doi.org/10.1021/cr500002z | Chem. Rev. XXXX, XXX, XXX−XXX

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