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Fast fabrication of long-range ordered porous alumina membranes by hard anodization

Nature Materials volume 5, pages 741–747 (2006)Cite this article

Abstract

Nanoporous anodic aluminium oxide has been widely used for the development of various functional nanostructures. So far these self-organized pore structures could only be prepared within narrow processing conditions. Here we report a new oxalic-acid-based anodization process for long-range ordered alumina membranes. This process is a new generation of the so-called ‘hard anodization’ approach that has been widely used in industry for high-speed fabrication of mechanically robust, very thick (>100 μm) and low-porosity alumina films since the 1960s. This hard anodization approach establishes a new self-ordering regime with interpore distances, (Dint)=200–300 nm, which have not been achieved by mild anodization processes so far. It offers substantial advantages over conventional anodization processes in terms of processing time, allowing 2,500–3,500% faster oxide growth with improved ordering of the nanopores. Perfectly ordered alumina membranes with high aspect ratios (>1,000) of uniform nanopores with periodically modulated diameters have been realized.

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Figure 1: Hard anodization versus mild anodization.
Figure 2: The effect of voltage on the self-ordering of AAO.
Figure 3: A new and second regime of self-ordering for oxalic acid anodization.
Figure 4: Long-range ordered alumina membranes with modulated pore diameters.

References

  1. Keller, F., Hunter, M. S. & Robinson, D. L. Structural features of oxide coatings on aluminium. J. Electrochem. Soc. 100, 411–419 (1953).

    Article  Google Scholar 

  2. Hunter, M. S. & Fowle, P. Determination of barrier layer thickness of anodic oxide coating. J. Electrochem. Soc. 101, 481–485 (1954).

    Article  Google Scholar 

  3. Thompson, G. E. & Wood, G. C. Porous anodic film formation on aluminium. Nature 290, 230–232 (1981).

    Article  Google Scholar 

  4. Lohrengel, M. M. Thin anodic oxide layers on aluminium and other valve metals: high field regime. Mater. Sci. Eng. R 11, 243–294 (1993).

    Article  Google Scholar 

  5. Diggle, J. W., Downie, T. C. & Goulding, C. W. Anodic oxide films on aluminium. Chem. Rev. 69, 365–405 (1969).

    Article  Google Scholar 

  6. Thompson, G. E., Furneaux, R. C., Wood, G. C., Richardson, J. A. & Goode, J. S. Nucleation and growth of porous anodic films on aluminium. Nature 272, 433–435 (1978).

    Article  Google Scholar 

  7. Wood, G. C. & O’Sullivan, J. P. The anodizing of aluminium in sulphate solutions. Electrochim. Acta 15, 1865–1876 (1970).

    Article  Google Scholar 

  8. Lee, W., Scholz, R., Nielsch, K. & Gösele, U. A template-based electrochemical method for the synthesis of multisegmented metallic nanotubes. Angew. Chem. Int. Edn 44, 6050–6054 (2005).

    Article  CAS  Google Scholar 

  9. Lee, S. B. et al. Antibody-based bio-nanotube membranes for enantiomeric drug separations. Science 296, 2198–2200 (2002).

    Article  Google Scholar 

  10. Park, S., Lim, J.-H., Chung, S.-W. & Mirkin, C. A. Self-assembly of mesoscopic metal-polymer amphiphiles. Science 303, 348–351 (2004).

    Article  CAS  Google Scholar 

  11. Kovtyukhova, N. I. & Mallouk, T. E. Nanowire p-n heterojunction diodes made by templated assembly of multilayer carbon-nanotube/polymer/semiconductor-particle shells around metal nanowires. Adv. Mater. 17, 187–192 (2005).

    Article  CAS  Google Scholar 

  12. Zhi, L., Wu, J., Li, J., Kolb, U. & Müllen, K. Carbonization of disclike molecules in porous alumina membranes: Toward carbon nanotubes with controlled graphene-layer orientation. Angew. Chem. Int. Edn 44, 2120–2123 (2005).

    Article  CAS  Google Scholar 

  13. Mikulskas, I., Juodkazis, S., Tomašiūmas, R. & Dumas, J. G. Aluminium oxide photonic crystals grown by a new hybrid method. Adv. Mater. 13, 1574–1577 (2001).

    Article  Google Scholar 

  14. Hurst, S. J., Payne, E. K., Qin, L. & Mirkin, C. A. Multisegmented one-dimensional nanorods prepared by hard-template synthetic methods. Angew. Chem. Int. Edn 45, 2672–2692 (2006).

    Article  CAS  Google Scholar 

  15. Masuda, H. & Fukuda, K. Ordered metal nanohole arrays made by a two-step replication of honeycomb structures of anodic alumina. Science 268, 1466–1468 (1995).

    Article  Google Scholar 

  16. Masuda, H., Hasegwa, F. & Ono, S. Self-ordering of cell arrangement of anodic porous alumina formed in sulphuric acid solution. J. Electrochem. Soc. 144, L127–L130 (1997).

    Article  Google Scholar 

  17. Li, A. P., Müller, F., Birner, A., Nielsch, K. & Gösele, U. Hexagonal pore arrays with a 50–420 nm interpore distance formed by self-organization in anodic alumina. J. Appl. Phys. 84, 6023–6026 (1998).

    Article  Google Scholar 

  18. Masuda, H., Yada, K. & Osaka, A. Self-ordering of cell configuration of anodic porous alumina with large-size pores in phosphoric acid solution. Jpn. J. Appl. Phys. 37, L1340–L1342 (1998).

    Article  Google Scholar 

  19. Shingubara, S., Morimoto, K., Sakaue, H. & Takahagi, T. Self-organization of a porous alumina nanohole array using a sulfuric/oxalic acid mixture as electrolyte. Electrochem. Solid-State Lett. 7, E15–E17 (2004).

    Article  CAS  Google Scholar 

  20. Li, F., Zhang, L. & Metzger, R. M. On the growth of highly ordered pores in anodized aluminium oxide. Chem. Mater. 10, 2470–2480 (1998).

    Article  Google Scholar 

  21. Nielsch, K., Choi, J., Schwirn, K., Wehrspohn, R. B. & Gösele, U. Self-ordering regimes of porous alumina: The 10% porosity rule. Nano Lett. 2, 677 (2002).

    Article  CAS  Google Scholar 

  22. Csokán, P. Beiträge zur kenntnis der anodischen oxydation von aluminium verdunnter, kalter schwefelsaure. Metalloberfläche 15, B49–B53 (1961).

    Google Scholar 

  23. Csokán, P. & Sc, C. C. Hard anodizing: Studies of the relation between anodizing conditions and the growth and properties of hard anodic oxide coatings. Electroplat. Metal Finish. 15, 75–82 (1962).

    Google Scholar 

  24. Lichtenberger-Bajza, E., Domony, A. & Csokán, P. Untersuchung der struktur und anderer eigenschaften von durch anodische oxydation auf aluminium erzeugten hartoxydschichten. Werkstoffe. Korros. 11, 701–707 (1960).

    Article  Google Scholar 

  25. Csokán, P. Some observations on the growth mechanism of hard anodic oxide coatings on aluminium. Trans. Inst. Metal Finishing 41, 51–56 (1964).

    Article  Google Scholar 

  26. Olbertz, B. Hartanodisieren eröffnet aluminum vielfältige technische Anwendungs-möglichkeiten. Aluminium 3, 268–270 (1988).

    Google Scholar 

  27. Rajendra, A. et al. Hard anodization of aluminium and its application to sensorics. Surf. Eng. 21, 193–197 (2005).

    Article  CAS  Google Scholar 

  28. John, S., Balasubramanian, V. & Shenoi, B. A. Hard anodizing aluminium and its alloys—AC in sulphuric acid—sodium sulphate bath. Met. Finish. 82, 33–39 (1984).

    Google Scholar 

  29. Hecker, J. G. Aluminum hard coats. Product Finishing 53, 88–92 (1988).

    Google Scholar 

  30. Ono, S., Saito, M., Ishiguro, M. & Asoh, H. Controlling factor of self-ordering of anodic porous alumina. J. Electrochem. Soc. 151, B473–B478 (2004).

    Article  CAS  Google Scholar 

  31. Chu, S. Z., Wada, K., Inoue, S., Isogai, M. & Yasumori, A. Fabrication of ideally ordered nanoporous alumina films and integrated alumina nanotubule arrays by high-field anodization. Adv. Mater. 17, 2115–2119 (2005).

    Article  CAS  Google Scholar 

  32. Ono, S., Saito, M. & Asoh, H. Self-ordering of anodic porous alumina induced by local current concentration: Burning. Electrochem. Solid-State Lett. 7, B21–B24 (2004).

    Article  CAS  Google Scholar 

  33. Ono, S., Saito, M. & Asoh, H. Self-ordering of anodic porous alumina formed in organic acid electrolytes. Electrochim. Acta 51, 827–833 (2005).

    Article  CAS  Google Scholar 

  34. Arrowsmith, D. J., Clifford, A. W. & Moth, D. A. Fracture of anodic oxide formed on aluminium in sulphuric acid. J. Mater. Sci. Lett. 5, 921–922 (1986).

    Article  Google Scholar 

  35. Wada, K., Shimohira, T., Yamada, M. & Baba, N. Microstructure of porous anodic oxide films on aluminium. J. Mater. Sci. Lett. 21, 3810–3816 (1986).

    Article  Google Scholar 

  36. Masuda, H. et al. Square and triangular nanohole array architectures in anodic alumina. Adv. Mater. 13, 189–192 (2001).

    Article  Google Scholar 

  37. Fournier-Bidoz, S., Kitaev, V., Routkevitch, D., Manners, I. & Ozin, G. A. Highly ordered nanosphere imprinted nanochannel alumina (NINA). Adv. Mater. 16, 2193–2196 (2004).

    Article  CAS  Google Scholar 

  38. Asoh, H., Nishio, K., Nakao, M., Tamamura, T. & Masuda, H. Conditions for fabrication of ideally ordered anodic porous alumina using pretextured Al. J. Electrochem. Soc. 148, B152–B156 (2001).

    Article  Google Scholar 

  39. Lee, W., Ji, R., Ross, C. A., Gösele, U. & Nielsch, K. Wafer-scale Ni imprint stamps for porous alumina membranes based on interference lithography. Small 2, 978–982 (2006).

    Article  CAS  Google Scholar 

  40. O’Sullivan, J. P. & Wood, G. C. The morphology and mechanism of formation of porous anodic films on aluminium. Proc. R. Soc. London A 317, 511–543 (1970).

    Article  Google Scholar 

  41. Jessensky, O., Müller, F. & Gösele, U. Self-organized formation of hexagonal pore arrays in anodic alumina. Appl. Phys. Lett. 72, 1173–1175 (1998).

    Article  Google Scholar 

  42. Parkhutik, V. P. & Shershulsky, V. I. Theoretical modelling of porous oxide growth on aluminium. J. Phys. D 25, 1258–1263 (1992).

    Article  Google Scholar 

  43. Ebihara, K., Takahashi, H. & Nagayama, M. Structure and density of anodic oxide films formed on aluminium in oxalic acid solutions. J. Met. Finish. Soc. Jpn 34, 548–553 (1983).

    Article  Google Scholar 

  44. Güntherschulze, A. & Betz, H. Die bewegung der ionengitter von isolatoren bei extremen elektrischen feldstärken. Z. Phys. 92, 367–374 (1934).

    Article  Google Scholar 

  45. Cabrera, N. & Mott, N. F. Theory of the oxidation of metals. Rep. Prog. Phys. 12, 163–184 (1948).

    Article  Google Scholar 

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Acknowledgements

We thank F. Müller for helpful discussions, D. Hesse for his comments on the manuscript and W. Gruner at the Leibniz-Institut für Festkörper- und Werkstoffforschung Dresden (IFW-Dresden) for chemical anaysis. We acknowledge financial support from the German Federal Ministry for Education and Research (BMBF, Project No. 03N8701).

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  1. Max Planck Institute of Microstructure Physics, Weinberg 2, D-06120, Halle, Germany

    Woo Lee, Ran Ji, Ulrich Gösele & Kornelius Nielsch

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Correspondence to Woo Lee.

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Lee, W., Ji, R., Gösele, U. et al. Fast fabrication of long-range ordered porous alumina membranes by hard anodization. Nature Mater 5, 741–747 (2006). https://doi.org/10.1038/nmat1717

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