IR SPECTROSCOPY OF Fe-TiO2, FILMS PREPARED BY MAGNETRON SPUTTERING

  • Vera А. Logachova Cand. Sci. (Chem.), Researcher, Voronezh State University; ph.: +7(4732) 208445, e-mail: kcmf@vsu.ru
  • Nikolay N. Afonin Dr. Sci. (Chem.), Professor, Voronezh State Pedagogical University; ph.: +7(473) 2208445, e-mail: nafonin@vspu.ac.ru
  • Anatoly N. Lukin Cand. Sci. (Phys.-Math.), Associate Professor of the Department of Solid State Physics and Nanostructures, Voronezh State University; ph.: +7(950) 7548707, e-mail: ckp_49@mail.ru
  • Leonid N. Nikitin Cand. Sci. (Eng.), Assistant Professor of the Department of Design and Production of Radio Equipment, Voronezh State Technical University; ph.: +7(473) 2437706, e-mail: l.n.nikitin@mail.ru
  • Julia А. Kiseleva the competitor for science degree of Master Science in Chemistry, Faculty of Chemistry, Voronezh State University; ph.: +7 (919) 2317692, e-mail: yulechka-kiseleva-93@mail.ru
Keywords: IR spectroscopy, magnetron sputtering, Fe-TiO2 film

Abstract

The doping of TiO2 films with various metals, including Fe, allows measuring the TiO2 band gap, which makes it possible to use the compounds for photovoltaic applications. The discussed research was aimed at studying the formation of complex oxides by IR spectroscopy on the surface and inside Fe-TiO2 films. The films were prepared by magnetron sputtering of iron on titanium oxide, followed by annealing in a diffractometer vacuum chamber at P = 1.33·10-2 Pa, vacuum reduction annealing at P = 10-4 Pa, and thermooxidation in flowing oxygen at atmospheric pressure.

The films were deposited on single-crystal silicon substrates with a Pt sublayer. Fe magnetron sputtering was conducted in a modernized vacuum unit UVN-1: the discharge was excited in 13.3·10-2 Pa high-purity argon. The discharge voltage was 420 V. A metal iron target with an impurity level lower than 0.01 at.% was used as a cathode. The sputtering rate was 7.2 nm/s. The thickness of the iron film was determined by the time of spluttering and was 120 nm.

The phase composition of Fe-TiO2 films was studied by X-ray powder diffraction using ARL X’TRA diffractometer. The reflectance-absorption (RAS) and total internal reflection (ATR) spectra of the films were measured with the help of the Vertex-70 infrared Fourier spectrometer by Brooker (Germany). The reflectance-absorption spectra were measured with a mirror reflection attachment with a 13-83° variable incidence angle. ATR spectra were measured with a single-pass Platinum-ATR with a diamond prism.

Films obtained under different annealing regimes were heterophase and contained: TiO2 in the rutile structure, two iron oxides – Fe3O4 and Fe2O3, and phases of complex oxides based on titanium and iron oxides: FeTiO3 (ilmenite) and Fe2TiO4 (ulvospinels).

The research demonstrated that the shift in the characteristic vibrations of the Ti-O bond toward lower frequencies can be explained by the presence of Fe+3 cations in the TiO2 crystal structure. It was established that the absorption bands caused by the deformation vibrations of the Fe-OH bond can only be observed in ATR spectra and are shifted toward higher frequencies (1.045 cm-1) compared to individual iron oxides, which indicates the formation of complex oxides in the Fe-TiO2 films.

The shift of the characteristic vibrations of Ti-O bond toward the lower frequencies during the modification of rutile by iron is caused by distortions in the symmetry of the Ti+4 coordination environment and indicates the presence of Fe+3 cations in the crystal structure.

ACKNOWLEDGMENTS

The results of the research were obtained using the equipment of VSU's Equipment Centre for Collective Use of Scientific Equipment

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References

1. Carneiroa J. O., Teixeiraa V., Portinhaa A., Magalhãe A., Coutinhob P., Tavaresa C. J., Newton R. Materials Science and Engineering: B, 2007. vol. 138, no. 8, pp. 144–150. doi: https://doi.org/10.1016/j.mseb.2005.08.130
2. Fujishima A., Honda K. Nature, 1972, vol. 238, pp. 37–40. doi:10.1038/238037a0
3. Zakrzewska K., Radecka M., Rekas M. Thin Solid Films, 1997, vol. 310, pp. 161–166. DOI: https://doi.org/10.1016/S0040-6090(97)00401-X
4. Al-Salim N. I., Bagshaw S. A., Bittar A., Kemmitt T., McQuillan A. J., Mills A. M., Ryan M. J. J. Mater. Chem, 2000. vol. 10, pp. 2358–2363. DOI: 10.1039/B004384M
5. Sood S., Umar A., Mehta S. K., KansalS. K. J. of Colloid and Interface Science. 2015, vol. 450, pp. 213–223. DOI: https://doi.org/10.1016/j.jcis.2015.03.018
6. Kaleji B. K., Sarraf-Mamoory R. Nakata K., Fujishima A. J. of Sol-Gel Science and Technology November, 2011, vol. 60, pp. 99. DOI: 10.1007/s10971-011-2560-2
7. Li F. B., Li X. Z., Hou M. F. Appl. Catal. B, 2004, vol. 48, no. 3, pp. 185-194. DOI: https://doi.org/10.1016/j.apcatb.2003.10.003
8. Wu Y., Lu G., Li S. Catalysis Letters, 2009, vol. 133, pp. 97-105. doi:10.1007/s10562-009-0165-y
9. Inorganic Chemistry. Chemistry of Elements, vol. 1. / Ed. by Yu. D. Tretyakovet al. Moscow, Akademkniga Publ., 2007, pp. 230, 421. (in Russia)
10. Ganesh I., Kumar P. P., Gupta A. K., Sekhar P. S. C., Radha K., Padmanabham G., Sundararajan G. Processing and Application of Ceramics, 2012, vol. 6, no. 1, pp. 21–36. DOI:10.2298/PAC1201021G
11. Hanaor D. A. H., Assadi M. H. N., Li S., Yu A., Sorrell C. C. Computational Mechanics, 2012, vol. 50, pp. 185-194. doi:10.1007/s00466-012-0728-4
12. Wantala K., Tipayarom D., Laokiat L., Grisdanurak N. Reaction Kinetics and Catalysis Letters, 2009, vol. 97. pp. 249-254. DOI 10.1007/s11144-009-0045-x
13. Logacheva V. A., Afonin N. N., Wachtel V. M., Kiseleva Yu. A., Sёmov Yu. G. Condensed Matter and Interphase, 2016, vol. 18, no. 3, pp. 345-355. Available at: http://www.kcmf.vsu.ru/resources/t_18_3_2016_005.pdf
14. Tolstoy V. P., et al. Handbook of Infrared Spectroscopy of Ultrathin Films. N.Y. Willey: 2003, pp. 671-673.
15. Davydov A. A. IR Spectroscopy in the Chemistry of the Oxide Surface. Novosibirsk, Science Publ., 1984, pp. 13-24. (in Russia)
16. Nakamoto K. Infrared and Raman Spectra of Inorganic and Coordination Compounds. Wiley, New York, 1986, 427 p.
17. Vasconcelos D. C. L., Costa V. C., Nunes E. H. M., Sabioni A. C. S., Gasparon M., Vasconcelos W. L. Materials Sciences and Applications, 2011, vol. 2, no. 10, pp. 1375-1382. DOI: 10.4236/msa.2011.210186
18. Phillippi C. M., Lyon S. R. Physical Review B, 1971, vol. 3, no. 6, pp. 2086-2087. DOI:https://doi.org/10.1103/PhysRevB.3.2086
Published
2017-11-07
How to Cite
LogachovaV. А., Afonin, N. N., Lukin, A. N., Nikitin, L. N., & KiselevaJ. А. (2017). IR SPECTROSCOPY OF Fe-TiO2, FILMS PREPARED BY MAGNETRON SPUTTERING. Kondensirovannye Sredy I Mezhfaznye Granitsy = Condensed Matter and Interphases, 19(2), 239-247. https://doi.org/10.17308/kcmf.2017.19/197
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