PAPER

www.rsc.org/nanoscale | Nanoscale

Tailoring morphology in free-standing anodic aluminium oxide: Control of barrier layer opening down to the sub-10 nm diameter
Jie Gong,a William H. Butlera and Giovanni Zangari*b
Received (in Cambridge, MA, USA) 26th January 2010, Accepted 28th January 2010 First published as an Advance Article on the web 18th March 2010 DOI: 10.1039/c0nr00055h Free-standing, highly ordered porous aluminium oxide templates were fabricated by three-step anodization in oxalic, sulfuric or phosphoric acid solutions, followed by dissolution of the aluminium substrate in HgCl2. Opening of the pore bottoms on the barrier layer side of these templates was carried out by using chemical or ion beam etching. Chemical etching is capable of achieving full pore opening, but partial pore opening occurs inhomogeneously. On the contrary, ion beam etching enables homogeneous and reproducible partial pore opening, with the pore size controlled through the etching time. By this method, pore openings as small as 5 nm can reliably be obtained.

1. Introduction
Nanoporous anodic aluminium oxide (AAO) is nding wide application as a template for the fabrication of one-dimensional nanostructures1 or two-dimensional patterns,26 as a photonic crystal,7 in nanouidics8 and ltration,9 in magnetic information storage,10 sensing,11 and even in biomedical applications such as drug delivery.12 AAO is formed by the electrochemical oxidation of aluminium (Al) in an appropriate acidic electrolyte, and consists of an array of parallel nanochannels perpendicular to the original Al surface, closed at the bottom by a hemispherical oxide lm known as the barrier layer.1315 AAO has been known for more than 50 years,16 but only after 1995, when Masuda and Fukuda reported the synthesis of a highly ordered pore array by two-step anodization in oxalic acid,2 its potential in nanofabrication was appreciated and related research efforts ourished. The self-organized pore growth process, leading to a densely packed hexagonal pore structure, is controlled through the electrolyte chemistry, applied voltage, and processing time. Self-organized growth has been achieved in oxalic,2,1719 sulfuric,1720 and phosphoric acids,18,19,21,22 and mixed oxalic and sulfuric acid solutions.23 Interpore distance and pore diameter can be varied between 50500 nm and 5300 nm, respectively, depending on the electrolyte and anodization voltage employed;18,24 in addition, the latter can be widened by chemical etching in diluted acids. Long range ordering of the porous structure can be achieved using a two or three-step anodization process2,25 or by pre-texturing the initial aluminium surface via nanoimprint,26,27 nanoindentation,28 or ion beam prepatterning.29
a Center for Materials for Information Technology, University of Alabama, Tuscaloosa, AL, 35487-0209 b Department of Materials Science and Engineering and CESE, University of Virginia, 395 McCormick Rd., P.O. Box 400745, Charlottesville, VA, 22904-4745, USA. E-mail: gz3e@virginia.edu; Tel: +1-434-243-5474 Electronic supplementary information (ESI) available: Current transients during anodization, SEM and AFM images of aluminium oxide anodized in sulfuric acid and phosphoric acid. See DOI: 10.1039/c0nr00055h Now at Seagate Technology, Research and Technology Development, 7801 Computer Avenue South, Bloomington MN 55435

Many applications of AAO in nanofabrication require opening of the pore bottom; this has been achieved by chemical etching in acidic solutions,30 ion beam31 or plasma etching.3 Complete removal of the pore bottom results in an opening with the same size as the channel; however, in some cases, close control over the diameter of the opening, below the channel diameter, may be required. This is particularly important, for example, in the fabrication of nanoconstrictions for magnetic point contacts32 or for the control of magnetic domain wall motion33 in spintronic applications, as well as in the synthesis of molecular membranes.34,35 Partial pore opening of oxalic acid anodized AAO by wet chemical etching has been recently reported;30 however, no detailed comparison of this process with ion beam etching has been carried out. Furthermore, although ion beam etching methods have demonstrated the uniform engraving of holes on the hemispherical shaped surface of the barrier layer with diameter as small as 10 nm using oxalic acid AAO,31 no such process has been reported for phosphoric or sulfuric acid AAO, which could produce larger or smaller nanoholes, respectively, due to the different size of the porous structures. In this work, free-standing sulfuric, oxalic and phosphoric acid AAO have been synthesized by a three-step anodization process, and the effects of chemical and ion beam etching on the morphology of sulfuric, oxalic and phosphoric acid AAOs with different pore sizes have been compared. It is demonstrated that uniformly engraved holes with diameter down to 5 nm can be reliably obtained using ion beam etching of sulfuric acid AAO. Fig. 1 depicts a schematic diagram of the barrier opening processes discussed in this paper, and provides a qualitative illustration of the resulting AAO nanostructures.

2. Experimental
Chemicals All chemicals used in this work were of analytical grade. All solutions were prepared, and rinsing as well as cleaning were performed, using Milli-Q water (resistivity 18.2 MU cm).
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2. The resulting oxide lm was dissolved in a solution containing 0.2 M H2CrO4 and 0.4 M H3PO4 at 6070  C for 520 min. 3. The substrate was re-anodized for more than 12 h to create long-range ordering. 4. Step 2 was repeated, with a duration of more than 30 min to dissolve the thick oxide lm formed in step 3. 5. The substrate was nally anodized for a varying period of time, depending on the thickness of the AAO lm desired.

Post-treatment and template fabrication

Fig. 1 Schematic view of the fabrication process of free-standing porous AAO with the barrier layer perforated by wet chemical or ion beam etching. (a) AAO after anodization; (b) chemical post treatment to remove the metallic Al support; (c) free-standing AAO before etching; (d) uniform controllable openings on the barrier side achieved by ion beam etching; and (e) non-uniform openings on the barrier side obtained by wet chemical etching. d1: constriction/opening size; tb: barrier layer thickness; dp: pore diameter.

Aluminium sheet pretreatment A high purity polycrystalline aluminium (Al) sheet sample (99.998%, Alfa Aesar) was rst degreased in a 5% NaOH solution at 60  C for 30 s, rinsed, and then neutralized in 1 : 1 HNO3 for 510 s. After thorough rinsing in water, the substrate was electropolished (Buehler Electropolisher-4, 32 V, 4560 s) in perchloric acidethanol electrolyte (165 mL 65% HClO4, 700 mL ethanol, 100 mL 2-butoxyethanol butylcellusove, and 137 mL H2O). The sheet was then washed, rst in warm and then in cold water. Atomic Force Microscopy AFM was utilized to characterize the topography and roughness of the polished surface. Aluminium anodization The pretreated Al sheet, with a polished active area of 3 cm2, was used as the anode during anodization. A degreased and neutralized 98.5% pure Al sheet with an area ten times larger (36 cm2) than the anode was used as the cathode. Anodization was performed under potentiostatic control, and the current transient during anodization was recorded by monitoring the voltage drop across a standard resistor (R 10 Ohm) connected in series. The temperature of the electrolyte was maintained at specic values using a jacketed beaker and a cooling system (Fisher Scientic, Model ISOTEMP 1016D Circulator). The solution was stirred vigorously using a magnetic stirrer in order to accelerate dispersion of the heat generated by the sample during anodization. Anodization was performed in one of three electrolyte systems, i.e. sulfuric (0.3 M, 3  C), oxalic (0.3 M, 15  C) or phosphoric acid (1 M, 3  C), to produce AAO lms with different geometries (different interpore distances and pore diameters). Highly ordered AAO templates were prepared using a multistep anodization process according to the following scheme:25 1. A polished Al sheet was anodized for 515 min to morphologically texture the Al surface.36
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To completely dissolve the metallic Al substrate without etching the AAO membrane, the highly ordered, supported AAO lm was carefully oated on the Al side on a saturated mercuric chloride (HgCl2) solution for 46 h (Fig. 1). Caution! HgCl2 is harmful if swallowed, inhaled or absorbed through skin. It should be handled with extreme care using goggles, lab coat and proper gloves. The AAO lm was gently rinsed and dried in vacuum over a desiccator (P2O5). The barrier layer was then controllably removed by chemical etching (CE) in 5% H3PO4 solution at room temperature (25  C) or by ion beam etching (IBE). A Veeco Microetch RF-1201 Ion Beam Etching System was employed for IBE. An inductively-coupled RF ion source was used, together with a Plasma Bridge Neutralizer (PBN) to keep the ion beam collimated. The ion beam etching chamber was rst pumped down to 78 107 torr, then Ar gas owed into the chamber at 20 sccm (standard cubic centimetre per minutes), keeping the chamber pressure constant at 1.321.34 104 torr. During etching, a 450 V beam voltage and 450 mA beam current were employed. Suppressor voltage was 300 V, and incident RF power was 300 W. PBN Ar gas ow rate was 3 sccm, and the ratio of neutralizer current/beam current (K factor) was 1.1. The ion beam incidence angle was 45 ; the sample xture was rotated at 0.1 revolutions per second and water cooled. The etching rate, calibrated using a Si wafer, was 40 nm min1. When converted to Al2O3 using a standard milling rate table, the etching rate was about 9 nm min1.

Characterization Scanning electron microscopy (SEM, Philips model XL 30) and atomic force microscopy (AFM, Digital Instruments, Dimension 3000) were employed to characterize the surface morphology and topography, respectively. The analyses using AFM were performed in tapping mode in air and the scan rate was kept at 1 Hz or lower. Mikromasch ultrasharp silicon cantilevers, with radius of curvature <10 nm, tip height of 1520 mm, full tip cone angle <20 , were used for AFM characterization. The regularity of the hexagonally patterned nanohole arrays was assessed quantitatively by fast Fourier transformation (FFT) of the AFM images, using the proprietary software (Nanoscope V) available with the AFM. The barrier side constriction size distribution after ion beam etching was evaluated by direct measurement of more than 50 openings in three AFM images taken at different locations.
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3. Results and discussion

3.1. Anodization process and sample characterization The purpose of the surface pretreatment is to clean and eliminate the main surface defects, while minimizing internal stresses present at the surface. The AFM surface topography after pretreatment is shown in Fig. S1 of the ESI. The surface appears smoother and glossier than before electropolishing. The rootmean-square (RMS) roughness as determined by AFM is 1.2 nm over a 4 4 mm2 area. Anodization was carried out under potentiostatic conditions in H2SO4, oxalic acid ((COOH)2) or H3PO4 solutions. Voltages were chosen in the range of values yielding long range order.18 Typical current densitytime (It) curves in H2SO4 for the rst and second anodization are shown in Fig. 2; the same plots for oxalic and phosphoric acid solutions are reported in Fig. S2 of the ESI. All curves show four stages of pore formation (Fig. 2, 1st anodization). In stage I, current drops abruptly due to the formation of the planar barrier oxide layer. In stage II, current gradually increases and after different time intervals (dependent on the solution and voltage applied) reaches its maximum between stages II and III. The increase in current is characteristic for porous AAO formation, indicating that eld-enhanced dissolution starts to concentrate at locally convex surface regions, nucleating the pores.25 In stage III, the current decreases slightly to a constant value, indicating that the rst initiated disordered pores are becoming hexagonally ordered, and stationary pore growth has been attained (stage IV).25 Comparison of the 1st anodization on the electropolished at surface and the 2nd anodization on the textured surface in the three electrolyte systems shows that the pore nucleation process (stage II) is greatly shortened on the textured surface. In addition, the lowest current on the at surface is always much lower than on the textured surface. This implies that pretexturing the surface accelerates the ordered pore initiation process. For both the 1st and 2nd anodization, the duration of regime II follows the trend H3PO4 (185 V) > (COOH)2 (40 V) > H2SO4 (26 V), which corresponds to the difculty of achieving ordering and the barrier layer thickness. The fabrication process and porous structure of AAO were studied in detail in H2SO4, (COOH)2 and H3PO4 solutions. The process parameters and extracted geometrical characteristics are

summarized in Table 1. Fig. 3(a) and (b) compare the topography, as determined by AFM, of the AAO surface after the 2nd and 3rd anodization in oxalic acid, respectively. Fast Fourier transform (FFT) patterns of the images, giving information about the structural periodicity in the inverse (momentum) space are shown in the corresponding insets. Both the AFM topography and the FFT patterns show that the number of defects decreases and the pore ordering improves after the 3rd anodization step. The diffraction ring and its broadening observed in the FFT of Fig. 3(a) indicate that 2D ordering of the structure is imperfect and that the interpore distance varies across the area of the sample. The barrier side topographic image (Fig. 3(c)), obtained by separation of the AAO membrane after the 3rd anodization step in saturated HgCl2, shows highly ordered, hexagonal patterns of hemispherical domes. The FFT images of the front and barrier side of AAO surfaces anodized three times consist of six equidistant and distinct spots, indicative of a perfectly ordered hexagonal pore lattice. Additional characterization and images of the AAO obtained in oxalic, sulfuric and phosphoric acid are available in the ESI. Similar to anodization on pre-textured Al substrates either by lithography22 or by nanoimprinting/nanoindentation,2628 a pore array pattern with double periodicity can, in principle, be obtained by rst anodizing in oxalic acid, then in sulfuric acid. The resulting morphology of the pore opening and barrier layer are shown in Fig. 4. Obviously, the pore-to-pore distance in the AAO obtained by anodization at a different voltage (2527 V) in sulfuric acid does not match the pitch of the pattern obtained in oxalic acid at 40 V. Therefore, the pores growing in the second stage will not follow the pre-patterned pits and a distorted pore arrangement will occur. The anodic pores produced in H2SO4 have a much higher density than the pre-existing pits, and are mostly located along the pattern ridges, with each pattern cell containing nearly the same number of pores. It is also interesting to note that, if the anodization sequence is reversed, i.e. anodizing in sulfuric acid followed by oxalic acid, the nal pattern shows the same features as after anodization in oxalic acid alone. 3.2. Barrier layer etching processes

The barrier layers present at the bottom of the pores of the AAO channels were opened by using one of two methods: wet chemical etching or ion beam etching. 3.2.1. Wet chemical etching (CE). The pore bottoms were opened by placing the AAO lm on the surface of a 5% H3PO4
Table 1 Process parameters and extracted geometric features for a typical three-step aluminium anodization in different electrolytes H2SO4 (26 V, 3  C) 5 1015 >12 3045 3.5 60 $3 1010 (COOH)2 (40 V, 15  C) 5 1015 >12 3045 6 108 $1 1010 H3PO4 (185 V, 3  C) 1520 >30 1620 120 7.5 450 50 $5 108

Process steps 1st anod. time/min 1st oxide strip time/min 2nd anod. time/h 2nd oxide strip time/min Growth rate/mm h1 Interpore distance/nm Pore density/cm2

Fig. 2 Typical anodization curves (current density vs. time, It) for twostep aluminium anodization in a sulfuric acid electrolyte (0.3 M H2SO4, 26 V, 3  C).

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Fig. 4 Double periodicity obtained by anodizing in oxalic acid (1st and 2nd step), followed by anodization in sulfuric acid (3rd step): (a) front side and (b) barrier side AFM surface topography, (c) SEM large area morphology.

Fig. 3 AFM surface topography of oxalic acid anodized AAO and the fast Fourier transform (FFT) patterns: (a) after 2nd anodization; (b) after 3rd anodization; (c) highly ordered hemispherical domes on the barrier side after dissolution of non-anodized aluminium.

solution, with the open side of the pores facing up, and the closed barrier layer side facing down and contacting the solution. Oxalic acid AAO lms were oated on the etching solution for 2540 min at room temperature (25  C); the SEM
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morphologies at different stages are shown in Fig. 5. CE can conveniently etch the barrier layer and fully expose the opened channels (Fig. 5(d)). However, it is difcult to controllably achieve across the entire surface partial opening of the holes on the barrier side, which would be essential when using this template to generate nano-constrictions of controlled diameter. In the intermediate stages of CE in fact (Fig. 5(b) and (c)), opened pores were distributed non-uniformly and the openings diameters varied over a wide range; under these conditions, a plot of the opening size vs. time would exhibit a large scattering and would provide limited information. As a comparison, the results of CE after various etching times for H2SO4-anodized AAO (Fig. 6) and H3PO4-anodized AAO (Fig. 7) are also shown. As expected, due to the different barrier layer thickness in the three cases, the times necessary to fully open the barrier caps are quite different. For H2SO4-anodized AAO, 2025 min of etching is sufcient (Fig. 6(d)); H3PO4anodized AAO on the other hand needs 240 min to fully open the pores (Fig. 7(b)). Again, CE can conveniently open the barrier layer to a full extent, but it does not allow accurate control of the size and location of the openings. As shown by AFM topography in Fig. 6(a1d1), CE generates a rough and irregular barrier side, resulting in inhomogeneous etching, and thus hindering prospective integration with other components. It is also interesting to note that, if the H3PO4-anodized AAO is over-etched, the walls of the AAO channels are etched at a much slower rate than the backbone, probably due to preferential anion incorporation at walls,15 or to differences in chemical composition27,30 or crystallinity15 between the inner and outer region. As a result, alumina bers can be produced, as also reported in ref. 37. Inhomogeneous pore etching by CE may be explained in terms of faster etching at defect sites (grain boundaries of the initial Al surface or boundaries of the ordered pore domains) or at regions with a thinner barrier layer. An initial, small difference in etching
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Fig. 6 AFM (a1d1) and SEM (a2d2) images of the barrier side of sulfuric acid-anodized AAO membranes after different etching times in 5% H3PO4 at room temperature (25  C): (a) 5 min; (b) 10 min; (c) 15 min; and (d) 20 min. The insets in (b2), (c2) and (d2) show enlarged views of the corresponding images.

Fig. 6 (b2) (probably a domain boundary), or Fig. 6 (c2) (probably a region with locally thinner barrier layer). 3.2.2. Ion beam etching (IBE). In order to controllably and uniformly engrave openings on the barrier side, and especially to decrease the size of the constrictions down to less than 10 nm, IBE was employed. In this instance, the AAO samples were carefully placed on a water-cooled rotary sample holder with steel clips, with the barrier layer side facing the ion source. During etching, the Ar+ ion incidence angle was tilted 45 from the surface normal and the sample xture was rotated, to ensure uniform etching. The AFM topography of oxalic acid-anodized AAO barrier side after different IBE processing times is shown in Fig. 8. Uniform and round holes (diameter 1530 nm) can be obtained
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Fig. 5 SEM surface morphology of the barrier side of oxalic acidanodized AAO after different etching times in 5% H3PO4 at room temperature (25  C): (a) 25 min; (b) 30 min; (c) 35 min; and (d) 40 min. The inset in (d) shows an enlarged view of the pore opening.

rate at separate locations may cause a local depletion of the etchant and preferential diffusion of the etchant from the bulk solutions to these regions, resulting in positive feedback. This effect may explain the clustering of opened pores observed in
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Fig. 7 SEM micrographs of the barrier side of phosphoric acid-anodized AAO membranes after different etching times in 5% H3PO4 at room temperature (25  C): (a) 220 min (left: tilted angle view; right: planar view; same scale bar); (b) 240 min (left and right image scans are at different magnications); (c) 260 min; and (d) 285 min.

over a large area when the etching time is limited to 510 min (Fig. 8(b) and (c)). Round hemispherical caps are uniformly milled from the top due to the uniform ux distribution of the ion beam. Chemical composition15 or stress38 gradients that may be present in the barrier layer at the pore bottom are of no consequence, since the energy differences involved due to these gradients are much smaller than the ion beam energy. Long-time etching leads to the disappearance of the protruding caps and results in holes with shape and diameter similar to the nanopores on the opposite side (Fig. 8(d)). This indicates that the

hemispherical barrier layer domes are completely etched away by the ion beam. Much smaller constrictions can be obtained by IBE from the barrier layer side of H2SO4-anodized AAO in shorter times. This is due to the fact that the pore size and the barrier thickness of these AAO samples are smaller. The morphologies resulting from the etching process are shown in Fig. 9 and 10. As shown in Fig. 9, very uniform small openings over a large area can be engraved on the barrier side. The opening size can be accurately controlled down to about 58 nm by limiting the etching time to 24 min. Increasing etching time results in increased opening size up to more than 18 nm, as well as a attened surface topography (Fig. 10). IBE of H3PO4-anodized AAO produces larger openings, ranging from 100 to 200 nm, as shown in Fig. 11. The etching time necessary to open the hemispherical domes is much longer now since the barrier layer is thicker in these samples. Although every dome in the images can be opened, the shape and size of the openings are not uniform on the same sample. This is probably a consequence of the fact that pores and barrier domes on phosphoric acid-anodized AAO are not as ordered as those obtained using the other acids. As shown in Fig. 11(c) and (d), triangular, trapezoidal, square and round openings can be found. The constriction size, dened as the full width at half depth of the AFM topographic scans across the barrier side openings, produced by ion beam etching on the three types of AAOs are extracted and summarized in Fig. 12. A broad range of constriction sizes can be obtained; in addition, the size distribution is narrow, with the exception of the H3PO4-anodized AAO. IBE processing of AAO, therefore, provides ideal templates to grow nanoconstrictions with closely controlled geometry, or to fabricate molecular membranes with closely controlled pore size in the deep sub-mm range.

Fig. 8 AFM surface topography of the barrier side of oxalic acidanodized AAO membranes after different ion beam etching times. (a) no etching; (b) 5 min (inset shows the enlarged 3D AFM image of a single cap); (c) 10 min; and (d) 15 min.

Fig. 9 AFM surface topography of the barrier side of sulfuric acidanodized AAO after different ion beam etching times: (a) 2 min; (b) 4 min; (c) 8 min; and (d) 12 min. Insets in (a)(d) show corresponding enlarged AFM images.

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Fig. 11 AFM (a1d1) and SEM (a2d2) images of the barrier side of phosphoric acid-anodized AAO membranes after different ion beam etching times: (a) no etching; (b) 50 min; (c) 80 min; and (d) 100 min. Insets in (a2)(d2) show tilted angle SEM views (same scale bar).

Fig. 10 AFM surface topography (top) and proles (bottom) of the barrier side of sulfuric acid-anodized AAO membranes after different ion beam etching times: (a) no etching, top height 8.3 nm; (b) 2 min, 3.9 nm; (c) 4 min, 3.1 nm; (d) 8 min, 2.7 nm; (e) 10 min, 2.1 nm; and (d) 12 min, 0 nm, the surface is completely attened by ion beam etching.

4. Conclusions
Free-standing sulfuric, oxalic and phosphoric acid-anodized AAO membranes, with pore diameter ranging from 20 to 400 nm, have been synthesized by a three-step anodization process and successive Al stripping. Chemical and ion beam etching were employed to open the pore bottoms of these AAO samples and their morphological characteristics were compared. Chemical etching conveniently enables full opening of the
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Fig. 12 Diameter of the opening obtained at the barrier layer by ion beam etching as a function of AAO type and ion beam etching time.

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channel array templates, however, locations of the opened regions and their size are difcult to control, particularly when partial pore opening is sought. These inhomogeneities appear to be a consequence of pre-existing non-uniformities and/or defects in the AAO barrier layer. Ion beam etching, on the other hand, is capable to engrave uniform holes on the barrier side, with pore size controllable by the etching time. Uniformly engraved holes, with diameter down to 5 nm, can be obtained using sulfuric acidanodized AAO and ion beam etching; this process has potential applications in the nanofabrication of constrictions with controlled size, down to the deep sub-mm range.

Acknowledgements
The support of NSF through grant NSF MRSEC DMR 0213985 is gratefully acknowledged.

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