Skip to main content Accessibility help

Photoelectrochemical properties of N-doped self-organized titania nanotube layers with different thicknesses

  • J.M. Macak (a1), A. Ghicov (a1), R. Hahn (a1), H. Tsuchiya (a1) and P. Schmuki (a1)...


The present work reports nitrogen doping of self-organized TiO2 nanotubular layers. Different thicknesses of the nanotubular layer architecture were formed by electrochemical anodization of Ti in different fluoride-containing electrolytes; tube lengths were 500 nm, 2.5 μm, and 6.1 μm. As-formed nanotube layers were annealed to an anatase structure and treated in ammonia environment at 550 °C to achieve nitrogen doping. The crystal structure, morphology, composition and photoresponse of the N-doped were characterized by scanning electron microscopy, x-ray diffraction, x-ray photoelectron spectroscopy, and photoelectrochemical measurements. Results clearly show that successful N-doping of the TiO2 nanotubular layers can be achieved upon ammonia treatment. The magnitude of the photoresponse in ultraviolet and visible light is strongly dependent on the thicknesses of the layers. This effect is ascribed to recombination effects along the tube length.


Corresponding author

a) Address all correspondence to this author. e-mail:


Hide All
1.Fujishima, A., Honda, K.: Electrochemical photolysis of water at a semiconductor electrode. Nature 238, 37 (1972).
2.Mills, A., Hunte, S.L.: An overview of semiconductor photocatalysis. J. Photochem. Photobiol., A: Chem. 108, 1 (1997).
3.ÓRegan, B.Grätzel, M.: A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films. Nature 353, 737 (1991).
4.Macak, J.M., Tsuchiya, H., Ghicov, A., Schmuki, P.: Dye-sensitized anodic TiO2 nanotubes. Electrochem. Comm. 7, 1133 (2005).
5.Anpo, M., Dohshi, S., Kitano, M., Hu, Y., Takeuchi, M., Matsuoka, M.: The preparation of highly efficient titanium oxide-based photofunctional materials. Ann. Rev. Mater. Res. 35, 1 (2005).
6.Wilke, K., Breuer, H.D.: The influence of transition metal doping on the physical and photocatalytical properties of titania. J. Photochem. Photobiol., A 127, 107 (1999).
7.Sakthivel, S., Kisch, H.: Daylight photocatalysis by carbon-modified titanium dioxide. Angew. Chem., Int. Ed. Engl. 42, 4908 (2003).
8.Lin, L., Lin, W., Zhu, X., Zhao, B., Xie, Y.: Phospor-doped titania—A novel photocatalyst active in visible light. Chem. Lett. (Jpn.). 34, 284 (2005).
9.Asahi, R., Morikawa, T., Ohwaki, T., Aoki, K., Taga, Y.: Visible-light photocatalyst in nitrogen-doped titanium oxides. Science 293, 269 (2001).
10.Kosowska, B., Mozia, S., Morawski, A., Grznil, B., Janus, M., Kalucki, K.: The preparation of TiO2–nitrogen doped by calcination of TiO2· xH2O under ammonia atmosphere for visible light photocatalysis. Sol. Energy Mater. Sol. Cells 88, 269 (2005).
11.Lindgren, T., Mwabora, J.M., Avendano, E., Jonsson, J., Hoel, A., Granvist, C.G., Lindquist, S.E.: Photoelectrochemical and optical properties of nitrogen doped titanium dioxide films prepared by reactive dc magnetron sputtering. J. Phys. Chem. B 107, 5709 (2003).
12.Zwilling, V., Aucouturier, M., Darque-Ceretti, E.: Anodic oxidation of titanium and TA6V alloy in chromic media. An electrochemical approach. Electrochim. Acta 45, 921 (1999).
13.Gong, D., Grimes, C.A., Varghese, O.K., Hu, W., Singh, R.S., Chen, Z., Dickey, E.C.: Titanium oxide nanotube arrays prepared by anodic oxidation. J. Mater. Res. 16, 3331 (2001).
14.Beranek, R., Hildebrand, H., Schmuki, P.: Self-organized porous titanium oxide prepared in H2SO4/HF electrolytes. Electrochem. Solid-St. Lett. 6, B12 (2003).
15.Macak, J., Tsuchiya, H., Schmuki, P.: High-aspect ratio TiO2 nanotubes by anodization of titanium. Angew. Chem., Int. Ed. Engl. 44, 2100 (2005).
16.Ghicov, A., Tsuchiya, H., Macak, J.M., Schmuki, P.: Titanium dioxide nanotubes prepared in phosphate electrolytes. Electrochem. Commun. 7, 505 (2005).
17.Taveira, L.V., Macak, J.M., Tsuchiya, H., Dick, L.F.P., Schmuki, P.: Initiation and growth of self-organized TiO2 nanotubes anodically formed in (NH4)2SO4/NH4F electrolytes. J. Electrochem. Soc. 152, B405 (2005).
18.Macak, J.M., Sirotna, K., Schmuki, P.: Self-organized porous titanium oxide prepared in Na2SO4/NaF. Electrochim. Acta 50, 3679 (2005).
19.Macak, J.M., Tsuchiya, H., Taveira, L., Aldabergerova, S., Schmuki, P.: Smooth anodic TiO2 nanotubes. Angew. Chem., Int. Ed. Engl. 44, 7463 (2005).
20.Macak, J.M., Tsuchiya, H., Bauer, S., Ghicov, A., Schmuki, P., Barczuk, P.J., Nowakowska, M.Z., Chojak, M., Kulesza, P.J.: Self-organized nanotubular TiO2 matrix as support for dispersed Pt/Ru nanoparticles; Enhancement of the electrocatalytic oxidation of methanol. Electrochem. Commun. 7, 1417 (2005).
21.Ghicov, A., Macak, J.M., Tsuchiya, H., Kunze, J., Haeublein, V., Kleber, S., Schmuki, P.: TiO2 nanotube layers: Dose effects during nitrogen doping by ion implantation. Chem. Phys. Lett. 419, 426 (2006).
22.Ghicov, A., Macak, J.M., Tsuchiya, H., Kunze, J., Haeublein, V., Frey, L., Schmuki, P.: Nitrogen-doped TiO2 nanotube arrays with strongly enhanced photoresponse in the visible range. Nano Lett. 6, 1080 (2006).
23.Vitiello, R.P., Macak, J.M., Ghicov, A., Tsuchiya, H., Dick, L.F.P., Schmuki, P.: N-doping of anodic TiO2 nanotubes using heat treatment in ammonia. Electrochem. Commun. 8, 544 (2006).
24.Beranek, R., Tsuchiya, H., Sugishima, T., Macak, J.M., Taveira, L., Fujimoto, S., Kisch, H., Schmuki, P.: Enhancement and limits of the photoelectrochemical response from anodic TiO2 nanotubes. Appl. Phys. Lett. 87, 243114 (2005).
25.Gärtner, W.W.: Depletion-layer photoeffects in semiconductors. Phys. Rev. 116, 84 (1959).
26.Johnson, E.J.: Semiconductors and Semimetals, Vol. 3 (Academic, New York, 1967), p. 153.
27.Dittrich, T.: Porous TiO2: Electron transport and application. Phys. Status Solidi A 182, 447 (2000).
28.Grätzel, M.: Photoelectrochemical cells. Nature 414, 338 (2001).
29.Saha, N.C., Tompkins, H.G.: Titanium nitride oxidation chemistry: An x-ray photoelectron spectroscopy study. J. Appl. Phys. 72, 3072 (1992).


Photoelectrochemical properties of N-doped self-organized titania nanotube layers with different thicknesses

  • J.M. Macak (a1), A. Ghicov (a1), R. Hahn (a1), H. Tsuchiya (a1) and P. Schmuki (a1)...


Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed