ARTICLE

Received 21 May 2014 | Accepted 2 Sep 2014 | Published 24 Oct 2014 DOI: 10.1038/ncomms6130

Ordered three-dimensional interconnected

nanoarchitectures in anodic porous alumina
Jaime Martı́n1,w, Marisol Martı́n-González1, Jose Francisco Fernández2 & Olga Caballero-Calero1

Three-dimensional (3D) nanostructures combine properties of nanoscale materials with

the advantages of being macro-sized pieces when the time comes to manipulate, measure
their properties or make a device. However, the amount of compounds with the ability to
self-organize in ordered 3D nanostructures is limited. Therefore, template-based fabrication
strategies become the key approach towards 3D nanostructures. Here we report the simple
fabrication of a template based on anodic aluminium oxide, having a well-defined, ordered,
tunable, homogeneous 3D nanotubular network in the sub 100-nm range. The 3D templates
are then employed to achieve 3D, ordered nanowire networks in Bi2Te3 and polystyrene.
Finally, we demonstrate the photonic crystal behaviour of both the template and the
polystyrene 3D nanostructure. Our approach may establish the foundations for future high-
throughput, cheap, photonic materials and devices made of simple commodity plastics,
metals and semiconductors.

1 Instituto de Microelectrónica de Madrid (IMM-CSIC), Calle de Isaac Newton 8, Tres Cantos, 28760 Madrid, Spain. 2 Instituto de Cerámica y Vidrio

(ICV-CSIC), Cantoblanco, 28049 Madrid, Spain. w Present address: Department of Materials and Centre for Plastic Electronics, Imperial College London,
SW7 2AZ London, UK. Correspondence and requests for materials should be addressed to J.M. (email: jaimemartinp@imm.cnm.csic.es) or to M.M.-G.
(email: marisol@imm.cnm.csic.es).

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A
pplications of nanomaterials would be undoubtedly gyroid 3D nanotubular network structures are frequently
ubiquitous, including areas from everyday life to the conformed in polymers as polystyrene (PS), poly(ethyleneoxide)
most advanced science, as they often present new or and so on, which present a working temperature o100 °C.
enhanced properties ascribed to their low dimensionality1. Furthermore, the low surface energy of polymeric templates
However, the practical employment of these nano-sized compo- (gpolymerso50 mN m  1) might hinder the infiltration of other
nents into a macroscale device, which must be manufactured in a low-surface-energy liquid compounds, such as most of the
factory, manipulated by an operator and used in a macroscale organic liquids—polymer solutions and melts, liquid crystals
world, is frequently hard to carry out. Therefore, the development and the like—into the tubular space. This would prevent making
of high-throughput nanotechnologies for real-life applications has 3D nanowire-like networks composed of many functional organic
been hitherto relatively slow. A promising strategy towards this materials.
goal is to integrate the nano-sized components into a large, In this work, we present the fabrication of a well-defined,
hierarchical structure up to the macroscale. Such a material controllable, homogeneous periodic 3D nanotubular network
would behave according to the properties of its individual over cm2 areas in anodic aluminium oxide (AAO), with tens of
nanocomponents—thus, low-dimensionality effects are micron thickness and high aspect-ratio. The produced template is
expected—while being a macroscale-size piece and, hence, easy composed of alumina, so it is mechanically, chemically and
to be manipulated and used. Three-dimensional (3D) nanowire- thermally stable and possesses high-surface-energy hydroxilated
like networks, having a hierarchical architecture comprised of pore walls, which may promote the infiltration of low-surface-
orderly interconnected nanowires, are a good example of these energy fluids. The 3D AAO presented here consists of a
kinds of materials. In fact, they are demonstrating enhanced hexagonal array of longitudinal nanopores, which are perpendi-
properties for many applications, as sensors2,3, electrochromic cularly interconnected through transversal nanochannels. Thus, it
devices4,5, solar cells6,7, energy storage8–10, scaffolds with special constitutes a perfectly ordered 3D nanoarchitecture in porous
mechanical properties11, optical elements12,13 and for alumina, in contrast to other analogous materials previously
electrocatalysis14. Hence, there exists a pressing need for 3D reported17–19. Such transversal nanochannels thus form networks
nanofabricated structures. confined into planes parallel to the alumina surface. The used
Nevertheless, despite the well-recognized potential of these fabrication approach is inspired by the ‘potentiostatic pulsed
kinds of 3D nanostructures, their use has been hitherto scarce anodization’ developed by Lee et al.20,21, in which mild
owing to the lack of scalable methods to synthesize/process anodization (MA) and hard anodization (HA) steps are
functional materials of the desired characteristics. For example, alternated20,22,23. However, in our approach, during HA steps
the macroscopic extension of 3D periodic nanostructures restricts the current is limited to a defined value. Then, we take advantage
their fabrication approaches to those compatible with an of the higher etching rates of the aluminium oxide grown under
affordable large-area production. Therefore, bottom-up fabrica- HA20 to attack selectively those regions, in such a way that
tion strategies, which exploit the self-organization of building longitudinal nanopores become interconnected with their first
blocks, turn out to be the most appropriate approaches. neighbours through transversal nanochannels. The amount and
Unfortunately, the amount of compounds that have the ability position of the pore-interconnecting junctions of the tubular
to self-organize in 3D periodic structures is limited15, which network can be precisely adjusted just by selecting the amount
avoids the direct employment of this approach for most of the and the length of the MA steps. Owing to the adjustable, dense
functional materials. A promising alternative method for periodic and ordered 3D nanoporous structure, the 3D AAOs presented
3D nanowire-like networks composed of those materials that do here can be used as templates for the fabrication of 3D periodic
not present self-organizing capabilities is the use of appropriate nanowire-like networks in a wide variety of materials with
templates. These templates must present, on one hand, the applications in thermoelectricity24, catalysis25, filtration26,
inverse morphology of the target nanostructure, that is, a 3D energy storage10 and photonics2 to name some. Moreover, we
nanotubular network, and, on the other hand, a macroscopic show here our results on the fabrication of 3D nanowire-like
extension. Thus, currently, the main challenge in the fabrication periodic nanostructures using 3D AAO templates. Thereby,
of 3D periodic nanowire-like networks is the development of 3D nanowire-like periodic nanostructures made of PS, by
versatile templates with periodic (ordered) 3D nanotubular in situ polymerization, and Bi2Te3, by electrodeposition, were
networks. fabricated27–29 to demonstrate the suitability of our templates to
Gyroid-forming block copolymers—with sacrificial continuous fabricate nanowire networks for both organic and inorganic
domains—have recently demonstrated to be efficient platforms to materials using different growth techniques. Finally, the one-
integrate 3D templates for the preparation of 3D nanostructures dimensional (1D) photonic crystal behaviour of both the 3D
in Au (ref. 12), NiO (ref. 5), V2O5 (ref. 10), TiO2 (ref. 16) by AAO and a 3D periodic nanowire-like network made of a
electrodeposition or sol–gel reactions. Likewise, 3D Pt nanowire commodity plastic as PS is demonstrated, which opens up the
networks have been also produced by electrodeposition within a possibility to produce high-throughput, cheap, photonic materials
track-etched polymer 3D membrane14. Both kinds of polymer and devices made of simple commodity plastics.
templates have shown their suitability for the growth of inorganic
compounds by non-aggressive, wet-chemical approaches.
However, growth methods yielding inorganic materials with the Results
best compositional and crystallographic features, which will Anodization processes. During a typical pulse anodization pro-
eventually present the best properties, such as, atomic layer cess, MA and HA constant voltage steps are periodically alter-
deposition, molecular beam epitaxy, chemical vapour deposition nated20,22,23. However, in our approach while constant voltage is
and the like, commonly imply/need aggressive reaction applied in MA steps, the current is limited to a defined value
conditions namely, high temperatures, high vacuum or presence during HA steps and thereof the voltage is not kept constant. The
of highly reactive species, which are hardly supported by polymer material is grown thus at a defined current during HA periods.
templates. Thus, block copolymer templates and most of the Then, the obtained AAO is selectively etched. As a consequence,
track-etched templates are not compatible with many of these the aluminium oxide grown under HA is partially removed, so
growth techniques, which avoids the nanostructuration of an that transversal nanochannels are formed, thus establishing the
important set of inorganic materials by this approach. Note that 3D porous network.

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NATURE COMMUNICATIONS | DOI: 10.1038/ncomms6130 ARTICLE

Since our aim is to achieve a periodic 3D structure, the transversal nanochannels of the desired dimensions (a few tens
ordering of the longitudinal pore arrangement must not be of nanometres). Furthermore, we observe that even if we do not
disturbed as a consequence of the alternation of HA and MA anodize exactly at a VHA,N giving rise to a Dint,long of 65 nm, a 2-s
steps. From a practical point of view, this means that the AAO pulse is too short a time for the system to lose its order—as shown
layers grown under MA conditions and under HA must present in Supplementary Fig. 2; Supplementary Note 2. Hence, a 3D
the same latticing parameter of the hexagonal pore arrangement AAO is achieved with a highly regular morphology. On the other
(Dint,long). Dint,long is proportional to the applied voltage in both hand, the length of the MA (tMA) steps is varied to tailor the
MA and HA regimes, but the proportionality coefficient, z, is distance between transversal nanochannels, as shown below.
different in each of them. The Dint,long is 65 nm for an AAO
grown in MA conditions under a voltage (VMA) of 25 V, so
that one should carry out the HA pulses at a voltage leading to The 3D AAO template. Figure 2a shows a representative scan-
the same Dint,long value. According to Schwrim et al.30, the ning electron microscope (SEM) image of a longitudinal fracture
relationship between Dint,long and the applied voltage in the surface of the 3D AAO template fabricated by pulse anodization
potentiostatic HA regime is zHA ¼ 1.8 nm V  1. Thus, the applied (VMA ¼ 25 V, tMA ¼ 100 s; VHA,N ¼ 32 V, tHA ¼ 2 s) and sub-
voltage during the pulses should be 36 V. However, we sequent partial chemical etching of the HA regions with H3PO4
experimentally observe that when applying pulses of 36 V 5 wt%, at 30 °C, for 18 min. Longitudinal pores laid on the vertical
without limiting the current intensity, we are not able to grow direction, while transversal nanochannel layers are arranged
3D AAO with a homogeneous porous structure, as the high along the horizontal and the out-of-plane directions of the image.
current during pulses induced severe damages in the structure— Thereby, the 3D nanochannel network in the 3D AAO consists of
probably due to heating effects. We managed to solve this a set of parallel longitudinal nanopores, such as those formed via
problem by limiting the intensity during the pulses (IHA) to a constant voltage anodization process in ‘common’ AAO tem-
55 mA (that is, a current density, j, of 27.5 mA cm  2). Moreover, plates, and transversal nanochannels, which interconnect adjacent
the current limitation assures that the kinetics of the reaction longitudinal nanopores at some periodic points. The tubular
during the pulses is almost independent of reaction time, so that network structure is thus similar to that of the illustration in
the same AAO thickness grows in each pulse (Fig. 1a). Note that Fig. 2b. The MA/HA-alternating layer structure of the 3D AAOs
the amount of material grown is directly proportional to j during induced the appearance of structural colour in the 3D AAO, as
anodization31,32. In contrast, when one directly pulses between both layers have different refracting indexes and are periodically
constant voltage during MA steps (VMA) and constant voltage alternated. The 3D AAO thus behaves as a distributed Bragg
during HA pulses, the current at the HA pulses (IHA) decreases reflector (DBR) or a 1D photonic crystal, as can be observed in
with time20 as the pore become longer and, thus, the growth of Fig. 2c, in which optical images of the 3D AAO acquired from
the AAO turns to be dependent of the anodization time, which different viewing angles are shown. The change in colour can be
leads to a non-homogeneous network structure in the AAO appreciated while rotating the sample. Such an alternating-
template (see Supplementary Fig. 1 and Supplementary Note 1). layered structure can be clearly appreciated in the cross-sectional
This issue is avoided by our procedure. Due to the limitation of SEM image in Fig. 2d.
current to 55 mA, the maximum voltage (VHA) reached during The dimensions of the structural features of a 3D AAO
the pulses is 31–31.5 V (see Fig. 1b), so we fix the nominal applied obtained after 60 MA/HA repetitions (VMA ¼ 25 V, tMA ¼ 100 s;
voltage for the pulses (VHA,N) to 32 V. The length of the pulse VHA,N ¼ 32 V, tHA ¼ 2 s) and the subsequent etching process in
(tHA) is established in 2 s, as we observe that the AAO layer grown H3PO4 5 wt%, at 30 °C, for 18 min are shown in Fig. 2d–f. The
during such a pulse is appropriate to afterwards develop total area of the 3D template is 2. In the direction perpendicular

30
a

20
j (mA cm–2)

10

0
32
b
30
V (V)

28

26

24
0.00 0.05 0.10 0.15 0.20 0.25 0.30
t (h)

Figure 1 | Pulse anodization. Current density–time (a) and voltage–time (b) transients during pulse anodization. The anodization process consists of a
periodic alternation of mild anodization (MA) steps followed by hard anodization (HA) steps. The maximum current density is fixed at 55 mA.

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ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms6130

40 nm
150 nm

35 nm
20 nm

HA MA
MA 65 nm
HA
MA

Figure 2 | 3D anodic alumina template. (a) Representative cross-section SEM image of the 3D AAO template fabricated by pulse anodization
(VMA ¼ 25 V, tMA ¼ 100 s; VHA,N ¼ 32 V, tHA ¼ 2 s) and subsequent partial chemical etching of the HA regions with H3PO4 5 wt%, at 30 °C, for 18 min. The
sample has being broken to see the cross-section more clearly. Scale bar, 5 mm. (b) Schematic cartoon of the interconnected nanochannel network
structure of the 3D AAO templates. (c) Optical photographs of a 3D AAO acquired from different viewing angles (the sample is suspended with tweezers).
The arrow indicates the rotation direction. (d) Cross-section micrograph of a 3D AAO template, in which the nanostructure of the template can be
appreciated. Scale bar, 500 nm. (e) Enlarged view of the area marked in d with a rectangle, in which both the longitudinal pores (in the vertical direction)
and the transversal pores (in the horizontal and in the out-of-plane direction of the image) can be distinguished. The distance between longitudinal
nanopores (Dint,long) is 65 nm, while the separation of the planes containing the transversal nanopores (Dint,trans) is 150 nm for this specific 3D AAO.
(f) Detailed view of the nanochannel structure from which the dimensions of different nanopores can be measured. The diameter of longitudinal nanopores
is 40 nm. The section of the transversal nanochannels is rather ellipsoid, presenting a short diameter of 20 nm and a large diameter of B35 nm.

to the template surface, the thickness of the 3D porous structure

Before etching After etching
is B20 mm (only about 10 mm are shown in Fig. 2a), but it can be
increased through a higher amount of MA/HA repetitions.
Hence, the whole 3D porous network has macroscale dimensions.
In contrast, the structure of the network is entirely nanoscopic.
The distance between longitudinal nanopores (Dint,long) is 65 nm,
while the distance between planes containing the transversal
nanopores (Dint,trans) is 150 nm for this specific 3D AAO example
(Fig. 2e). Longitudinal nanopores present a diameter of 40 nm
due to the pore-widening process (originally, pores that are 25 nm
in diameter are obtained), as observed in Fig. 2f. In such
micrographs, longitudinal nanopores lay vertically and the
transversal nanochannels lay out-of-plane of the image. The
diameter of transversal nanochannels depends on the chemical
etching process. For the typical etching process indicated above, Figure 3 | Formation of the 3D porous network. Cross-sectional SEM
the section of the transversal nanochannels is rather ellipsoid, image of a 3D AAO prepared by pulsed anodization before (a) and after
presenting a short diameter of 20 nm and a large diameter of (b) the chemical etching process in H3PO4 (H3PO4 5 wt%, at 30 °C, for
B35 nm (Fig. 2f). 18 min). Scale bar, 500 nm.
Although the 3D porous architecture in 3D AAOs is a
consequence of the pulsed anodization, only 1D longitudinal
nanopores are originally formed due to the anodization process,
next neighbour, without significantly affecting the longitudinal
as can be observed in Fig. 3a. However, the alumina grown
nanopore regions formed under MA steps, thus creating trans-
under HA conditions is chemically less stable than that grown
versal nanochannels between longitudinal nanopores (Fig. 3b).
under MA conditions, as found by Lee et al.20 Thereby, the
chemical etching rate of the alumina grown under HA is
significantly higher than of that grown under MA. In this way, Geometry of the 3D network. Longitudinal pores are orderly
when the AAO is attacked with an acid solution, AAO regions fashioned due to the fact that both the first anodization and the
formed during the HA pulse are preferentially dissolved. Hence, MA steps of the pulse anodization is carried out in self-ordering
one may preferentially widen the longitudinal nanopores in conditions (25 V, 0 °C, 0.3 M H2SO4) (Supplementary Fig. 2;
the HA regions until each longitudinal pore collapses with the Supplementary Note 2). This hexagonal pore distribution is not

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disturbed by the HA steps, as can be observed in the well-defined 3D porous structure at a local scale, the achieved
Supplementary Fig. 2c. Therefore, longitudinal nanopores are porous network lacked structural homogeneity along both the in-
completely parallel along the entire thickness of the template. plane and the cross-plane directions, due to the fact that the
To assess the geometry of the transversal nanochannel formation of the network is a consequence of self-induced current
network, we analyse the morphology of an internal MA terrace oscillations, which are difficult, if not infeasible, to be controlled.
after the detachment of the upper layers (Fig. 4a). A close view of Therefore, one cannot adjust the period, the shape and the
its surface (Fig. 4b) reveals that the transversal nanochannels amplitude of the diameter modulations by their approach and, in
conform a 2D porous network of hexagonal symmetry (see also consequence, neither the morphology of the 3D porous network.
Supplementary Fig. 3; Supplementary Note 2). This is obviously a Furthermore, the AAO template they obtained presented a
consequence of the hexagonal order of the longitudinal nanopore thickness distribution over the film. Likewise, in Losic’s19,33 and
array. Hence, the nanoporous network of the 3D AAO consists of Wang’s18 approach, the non-perfect organization of longitudinal
a hexagonal array of longitudinal nanopores, which are pores together with lengthy etching treatments required for
perpendicularly interconnected through the transversal nano- interconnecting the longitudinal pores led to severe structural
channel network, presenting also hexagonal symmetry (see also damages in the material. On the contrary, one can precisely adjust
(Supplementary Fig. 4). the amount and position of the pore-interconnecting junctions of
We have tried to extract further information about the HA the tubular network through our approach, just by selecting the
layer by means of ellipsometry (Supplementary Figs 5 and 6), amount and the length of the MA regions, as it can be observed in
which gives access to its refractive index and thus can be related Fig. 5. Moreover, since every single step in the anodization
to morphological parameters such as the porosity of the layer. For processes is well controlled and homogeneous, we can achieve
that, a sample is fabricated containing a single transversal well-defined 3D porous structures with no structural defects.
nanochannel plane sandwiched between two MA layers, and the Thereby, we fabricate 3D AAOs having different distances
ellipsometric data were fixed with a five-layer model that took the between transversal nanochannel regions/planes. Figure 5b,d,f
fundamental parameters (as described in the Supplementary Note shows 3D AAOs in which such a distance is tailored to 620 nm
3). The obtained porosity for the HA layer accounts to 75%. (tMA ¼ 530 s, Fig. 5a), 320 nm (tMA ¼ 180 s, Fig. 5b) and 150 nm
(tMA ¼ 100 s, Fig. 5c), respectively. Moreover, one can also
prepare a single 3D AAO with different distances between
Tuning geometry of the 3D nanoporous network. In contrast to transversal nanopores, such as that shown in Fig. 5h. Note that by
previous attempts to fabricate 3D structures in AAO, the proce- tailoring the amount and position of the transversal nanopores we
dure presented in this work allows a precise control over the modulate the density of integration of the eventual 3D periodic
morphology of the material. In the approach by Lee et al.17 the nanowire-like network formed within the 3D AAO, with the
spontaneous current oscillations taking place during the HA subsequent modulation of its properties (optical, mechanical,
process in oxalic acid electrolyte induced pore diameter thermoelectric and so on).
modulations, which can be eventually used to prepare a
3D porous network. Nevertheless, although they showed a
3D nanostructures composed of functional materials. Finally,
we show here our results on the fabrication of 3D nanostructures
using the 3D AAO templates. 3D nanowire-like periodic nanos-
tructures made of Bi2Te3 and other polymers such as PS have
been fabricated27–29 to demonstrate the suitability of our
templates both to grow 3D organic and inorganic materials.
Figure 6a,b shows the cross-sectional SEM images of a 3D
AAO containing a Bi2Te3 3D periodic nanowire-like network
prepared by pulsed electrodeposition34. Figure 6c shows an
optical photograph of the material, in which the green-coloured
area is where the Bi2Te3 was grown and the yellow areas
correspond to the gold substrate used as an electrode. The scale
bar corresponds to 1 cm in this image. Note the change in colour
due to the Bi2Te3 nanowire network as compared with empty 3D
AAO (Fig. 2c) or the black colour when nanowires are prepared
in a conventional AAO template.
Moreover, a 3D nanowire-like network is also fabricated in PS.
Figure 6d shows the cross-section of such a material after the
removal of the 3D AAO template in NaOH. Thus a freestanding
network of nanowires is shown as is represented in Fig. 6e. Note
that the greenish colour of Fig. 6f is due exclusively to the
nanoarchitecture, since bulk PS is transparent. The scale bar
corresponds to 1 cm in this image. This example constitutes a
clear demonstration of the efficacy of our template to nanos-
tructure low-surface-energy materials.
Other examples of functional polymers infiltrated in 3D AAO
templates are shown in Fig. 7. Figure 7a shows a set of
Figure 4 | Geometry of transversal nanochannels. (a) SEM micrograph of photographs (from different viewing angles) of the conju-
a fracture of a 3D AAO showing a MA terrace after the detachment of the gated polymer poly[[9-(1-octylnonyl)-9H-carbazole-2,7-diyl]-2,5-
upper layers. Scale ba, 1 mm. And, (b) the transversal nanochannel networks thiophenediyl-2,1,3-benzothiadiazole-4,7-diyl-2,5-thiophenediyl]
present a hexagonal symmetry as illustrated in the detailed view. Scale bar, (PCDTBT) inside 3D AAO (VMA ¼ 25 V, tMA ¼ 180 s, VHA,N ¼ 32
200 nm It can be observed they are well aligned. V, tHA ¼ 2 s). The different colours observed as a function of the

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30

j (mA cm–2)
20 620 nm

10

20 320 nm
j (mA cm–2)

10

0
e
150 nm
20
j (mA cm–2)

10

0
g
150 nm
20
j (mA cm–2)

620 nm
10

0
0 4 8 12 16
t (min)

Figure 5 | Modulation of the distance between transversal nanochannels. I–t transients of pulsed anodizations in which the tMA has been varied:
(a) tMA ¼ 530 s, (c) tMA ¼ 180 s, (e) tMA ¼ 100 s. (g) The I–t plot of a pulsed anodization in which two different tMA have been applied: tMA, 1 ¼ 100 s and
tMA, 2 ¼ 530 s. SEM images of the AAOs obtained thereof are shown in b,d,f and h, respectively. The distance between transversal nanochannels
are: (b) 620 nm (tMA ¼ 530 s), (d) 320 nm (tMA ¼ 180 s) and (f) 150 nm (tMA ¼ 100 s). When two distinct tMA are applied, an AAO with two different
separations between transversal nanochannels can be prepared, as evidenced in h. Scale bars, 500 nm.

eye angle are the direct consequence of the diffraction grating gap centred at E650 nm, as corresponding to a periodicity of
generated by the PCDTBT-filled transversal nanochannels and E320 nm (see the SEM micrograph in Fig. 8b). Note that an
the alumina layers (Supplementary Movie 1, recorded with a analogous porous alumina having only longitudinal nanopores
cellphone). More examples of light-emitting materials prepared (named as ‘common AAO’) shows an almost flat reflectance
by infiltrating conjugated polymers such as the copolymer based (Fig. 8c) and transmittance spectra (Supplementary Fig. 7). Thus,
on fluorene, thiophene and benzothiazole, poly(3-ethyl acetate the 3D AAOs enable one to easily fabricate highly tunable DBRs
thiophene-2,5-diyl), poly(phenylene vinylene)) into 3D AAOs in which both the distance between the alternating layers and the
are presented in Fig. 7b. The photographs are acquired under refraction index can be fully modulated. The periodicity can be
black light. Finally, composite materials showing complex easily modulated through the length of the MA periods, while the
response—electrical and optical for instance—can be prepared refraction index can be tuned by infiltrating the 3D template with
by infiltrating an electroactive polymer—such as the ferroelectric materials having the desired refractive index, such as polymers
poly(vinylidene flouride-co-trifluoroethylene)—into the 3D AAO from solutions (for example, following the approach showed in
(Fig. 7c). the Fig. 7). Note that this 3D AAO might also serve to fabricate
better DBR and anisotropic 3D photonic structures, as its pho-
tonic properties will be different in the in-plane and cross-plane
Optical properties of the 3D AAO and nanowire networks. directions. But, more interesting are the optical properties of the
The optical properties of the 3D AAO were investigated by 3D nanowire networks fabricated from the 3D AAO. We
ultraviolet–visible spectroscopy. The reflectance spectrum demonstrate here that by employing 3D AAOs, one can easy
obtained from a 3D AAO constructed on a glass substrate is seen produce cheap 1D photonic crystals, even made of a ‘simple’ and
in Fig. 8a. The distance between transversal nanochannels was popular commodity plastic as PS. Figure 8d shows the reflectance
320 nm in this sample, whereas the number of MA/HA bilayers spectrum of the PS 3D nanowire network shown in Fig. 8e. Again,
amounted to 60. Both the reflectance and transmittance spectra an intense reflection band at E525 nm can be observed as a
(in the Supplementary Fig. 7) show a well-defined optical band consequence of the alternation of layers with different refractive

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Longitudinal nanowires
Transversal nanowires

Air

Figure 6 | 3D Bi2Te3 and 3D PS nanostructured materials. (a,b) Cross-sectional SEM micrographs of a three-dimensional periodic nanostructure
(3D periodic nanostructures) of the semiconductor Bi2Te3 electrodeposited inside a 3D AAO template (VMA ¼ 25 V, tMA ¼ 180 s, VHA,N ¼ 32 V, tHA ¼ 2 s).
Scale bars, 500 nm. (c) Optical photograph of the template after Bi2Te3 filling, the black bar is 1 cm. (d) Cross-sectional SEM micrograph of a
three-dimensional periodic nanostructure (3D-periodic nanostructures) of polystyrene (PS) after removal of the 3D AAO (VMA ¼ 25 V, tMA ¼ 180 s,
VHA,N ¼ 32 V, tHA ¼ 2 s). Scale bars, 500 nm. (e) Sketch of the observed interconnected nanowire array. And (f) optical photograph of the freestanding
polystyrene 3D nanowire network after alumina removal, the black bar is 1 cm.

PCDTBT
PCDTBT

PFO-DTBT

P3EAT

P(VDF-TrFE)

Figure 7 | 3D AAO-functional polymer composite materials. (a) Optical images of a 3D AAO (VMA ¼ 25 V, tMA ¼ 180 s, VHA,N ¼ 32 V, tHA ¼ 2 s) infiltrated
with PCDTBT polymer observed from different rotation angles. A video recorded with a cellphone can be found in the Supplementary Movie 1.
(b) Photographs of 3D AAO templates infiltrated with different conjugated polymers acquired under dark light. From top: PCDTBT, a copolymer based on
fluorene, thiophene and benzothiazole (PFO-DTBT), poly(3-ethyl acetate thiophene-2,5-diyl) (P3EAT) and poly(phenylene vinylene) (PPV). Scale bars,
1 cm. (c) Photographs of a 3D AAO template infiltrated with the ferroelectric polymer poly(vinylidene flouride-co-trifluoroethylene) (PVDF-TrFE).
Scale bars, 1 cm.

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ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms6130

100 100
AAO3D PS 3D

80 80

Reflectance (%)
Reflectance (%)
60 60

40 40

20 20

0 0
450 500 550 600 650 700 750 400 450 500 550 600 650 700 750
Wavenlength (nm) Wavelength (nm)

100 100
Normal AAO
Bulk PS
80 80
Reflectance (%)

Reflectance (%)
60 60

40 40

20 20

0 0
500 600 700 400 500 600 700
Wavelength (nm) Wavelength (nm)

Figure 8 | Optical properties of 3D nanostructuctures. (a) Reflectance spectrum obtained from the 3D AAO shown in b. (c) Reflectance spectrum of an
AAO without transversal nanocannels (named as ‘common AAO’). (d) Reflectance spectra of the PS nanowire network shown in e. (f) Reflectance
spectrum of a non-porous PS (named as ‘bulk PS’). Scale bars in SEM micrographs correspond to 500 nm.

indices. This reflection band at E525 nm is responsible for the transversal nanochannels, which is ellipsoid, presents a short
strong green colour of this PS piece. Note that bulk PS is abso- diameter of 20 nm and a large diameter of B35 nm.
lutely colourless. The PS nanowire network was prepared form a 3D AAOs serve as templates for the fabrication of 3D periodic
3D AAO having a periodicity of E320 nm; however, the band nanowire-like networks in a wide variety of materials with
gap in the PS 3D nanostructure is blue-shifted (E525 nm) applications in thermoelectricity, catalysis, filtration, energy
probably as a consequence of a shrinkage or relaxation process of storage, photonics and the like. Thereby, we show the first
the nanostructure after the 3D AAO template removal. attempts to the fabrication of 3D periodic nanowire-like
nanostructures made of PS and Bi2Te3, as well as 3D composite
nanostructures comprised of functional polymers. The develop-
Discussion ment of such a versatile, rapid, low-cost, industrially scalable
A nanoporous AAO template has been prepared having a well- processing route that allows efficient and controlled deposition of
defined and homogeneous periodic 3D nanotubular network. The materials into structures with complex behaviour and complex
used fabrication approach includes a new type of pulsed geometries—Al pieces having any shape can be anodized—can be
anodization process, in which MA and HA pulses are alternated. expected to impinge on a variety of fields, from information
The voltage here is maintained constant during MA steps, while lighting, to sensing, to coating, to biomedicine. Thereby, we have
during HA pulses the current is limited to a fixed value. This demonstrated the 1D photonic crystal behaviour of both the 3D
current limitation is responsible for the high uniformity of the 3D AAO and a 3D periodic nanowire-like network made of a
nanostructure over the macroscopic piece, which yields a real 3D commodity plastic such as PS. Hence, through these new
ordered nanostructure. The preferential chemical etching of the materials and procedures, we might be presenting here the
aluminium oxide grown under HA regime led then to the foundations for future high-throughput, cheap, photonic materi-
formation of transversal nanochannels, which interconnect als and devices made of simple commodity plastics.
adjadcent longitudinal nanopores. The 3D AAO thus formed
consists of a hexagonal array of longitudinal nanopores,
Methods
perpendicularly interconnected through transversal nanochan- Preparation of the 3D AAO templates. The 3D-AAO templates were prepared
nels. 3D nanoporous networks with a thickness 420 mm in the by a two step anodisation method35, in which the second step was a pulsed
template cross-plane direction are prepared, but size limitation on anodisation process. To begin with, ultrapure (99.999%) aluminium foils (Advent
this matter is not expected. Likewise, the lateral extension of the Research Materials, England), were cleaned and degreased by sonication in acetone,
water, isopropanol and ethanol. Foils were then electropolished in a solution of
network prepared is in the order of cm2 and limitations are perchloric acid/ethanol (1/3) under a constant voltage of 20 V for 4 min. After that,
neither expected. The number and the distance between planes the first anodization was achieved for 24 h. A 0.3-M sulphuric acid (Panreac AC
containing the transversal nanopores can be precisely tailored Quı́mica, Spain) solution was used under a voltage of 25 V and at 0 °C. Then, the
selecting the amount and the length of the MA steps, which allow first anodic layer was removed by chemical etching in a mixture of phosphoric acid
(7 wt%) and chromic oxide (1.8 wt%). A pulsed anodization process was then
the modulation of the pore density of the templates. The distance carried out in the conditions specified along the text. Afterwards, the underlying
between longitudinal nanopores is 65 nm. The diameter of aluminium substrate was etched with an acidic solution of CuCl2 at 1 °C and the
longitudinal nanopores is 40 nm, while the section of the barrier layer was dissolved using a 10 wt% aqueous H3PO4 solution at 30 °C.

8 NATURE COMMUNICATIONS | 5:5130 | DOI: 10.1038/ncomms6130 | www.nature.com/naturecommunications

& 2014 Macmillan Publishers Limited. All rights reserved.
NATURE COMMUNICATIONS | DOI: 10.1038/ncomms6130 ARTICLE

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Acknowledgements
We would like to acknowledge financial support from ERC 2008 Starting Grant ‘Nano-
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anodization of aluminum under potentiostatic conditions. Adv. Funct. Mater. connected nanoarchitectures in anodic porous alumina. Nat. Commun. 5:5130
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