Hostname: page-component-586b7cd67f-l7hp2 Total loading time: 0 Render date: 2024-11-27T23:05:46.442Z Has data issue: false hasContentIssue false

Stoichiometry and microstructural effects on electrical conduction in pulsed dc sputtered vanadium oxide thin films

Published online by Cambridge University Press:  31 January 2011

Bryan D. Gauntt*
Affiliation:
Department of Materials Science and Engineering, Pennsylvania State University, University Park, Pennsylvania 16802
Elizabeth C. Dickey
Affiliation:
Department of Materials Science and Engineering, Pennsylvania State University, University Park, Pennsylvania 16802
Mark W. Horn
Affiliation:
Department of Engineering Sciences and Mechanics, Pennsylvania State University, University Park, Pennsylvania 16802
*
a) Address all correspondence to this author. e-mail: [email protected]
Get access

Abstract

Vanadium oxide thin films were deposited using pulsed direct current (dc) magnetron sputtering in an atmosphere containing argon and oxygen. The total pressure was varied from 2.5 to 15 mTorr, and the oxygen-to-argon ratio was varied from 2.5 to 30%. The resulting films were characterized using Rutherford backscattering spectroscopy (RBS), transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS), and glancing incidence x-ray diffraction (GIXRD). Electrical resistivity was calculated from IV curves acquired from two-point-probe measurements and thicknesses measured from bright-field TEM images of cross-sectioned samples. TEM and GIXRD were used to characterize the crystallinity of each film. A transition from nanocrystalline to amorphous growth was observed with increasing partial pressure of oxygen. In all samples, the only crystalline phase observed was cubic vanadium oxide with the sodium chloride structure. Though the cubic VOx equilibrium phase field is limited to a maximum of x = 1.3, the cubic phase was observed with a value of x up to 2 in the present work. It was apparent from electron diffraction data that increased oxygen content correlated with an increase in the film disorder. The increase in oxygen content also corresponded with an increase in the film resistivity, which varied over 7 orders of magnitude from 1.18 × 10−3 to 2.98 × 104 Ω·cm. The temperature coefficient of resistance was found to increase with increasing oxygen content from −0.1 to −3.5%/°C. A direct correlation between film disorder and temperature coefficient of resistivity (TCR) was observed and could be exploited to engineer materials with the desired TCR.

Type
Articles
Copyright
Copyright © Materials Research Society 2009

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

1Kruse, P.W. and Skatrud, D.D.: Uncooled Infrared Imaging Arrays and Systems (Academic Press, San Diego, CA, 1997), p. 341.Google Scholar
2Kasap, S.O.: Principles of Electronic Materials and Devices, 3rd ed. (McGraw-Hill, Boston, 2006), p. 874.Google Scholar
3Kruse, P.W.: Uncooled Thermal Imaging; Arrays, Systems, and Applications (SPIE Press, Bellingham, WA, 2002), p. 89.Google Scholar
4Alloy Phase Diagrams, edited by Baker, H. (ASM International, Materials Park, OH, 1992), p. 512.Google Scholar
5Schwingenschlögl, U. and Eyert, V.: The vanadium Magneli phases Vn O2n1. Ann. Phys. 13, 475 (2004).CrossRefGoogle Scholar
6Wada, H., Nagashima, M., Oda, N., Sasaki, T., and Mori, T.: VOX film, wherein X is greater than 1.875 and less than 2.0, and a bolometer-type infrared sensor comprising the VOX film. U.S. Patent No. 5,801,383. (September 1, 1998).Google Scholar
7Wang, S.B., Zhou, S.B., Huang, G., and Yi, X.J.: VOx thin films obtained by ion beam sputtering and oxidation processes. Surf. Coat. Technol. 191, 330 (2005).CrossRefGoogle Scholar
8Chain, E.: The influence of deposition temperature on the structure and optical properties of vanadium oxide films. J. Vac. Sci. Technol. A 4, 432 (1986).CrossRefGoogle Scholar
9Chain, E.: Effects of oxygen in ion-beam sputter deposition of vanadium oxide. J. Vac. Sci. Technol. A 5, 1836 (1987).CrossRefGoogle Scholar
10Wang, H., Yi, X., and Chen, S.: Low temperature fabrication of vanadium oxide films for uncooled bolometric detectors. Infrared Phys. Technol. 47, 273 (2006).CrossRefGoogle Scholar
11Duchene, J., Terraillon, M., and Pailly, M.: RF and DC reactive sputtering for crystalline and amorphous VO2 thin film deposition. Thin Solid Films 12, 231 (1972).CrossRefGoogle Scholar
12Kwan, C., Griffiths, C., and Eastwood, H.: Transport and structural properties of VO2 films. Appl. Phys. Lett. 20, 93 (1972).CrossRefGoogle Scholar
13Griffiths, C. and Eastwood, H.: Influence of stoichiometry on the metal-semiconductor transition in vanadium dioxide. J. Appl. Phys. 45, 2201 (1974).Google Scholar
14Wang, X., Li, H., Fei, Y., Xiong, Y., Nie, Y., and Feng, K.: XRD and Raman study of vanadium oxide thin films deposited on fused silica substrates by RF magnetron sputtering. Appl. Surf. Sci. 177, 8 (2001).CrossRefGoogle Scholar
15Hansen, S. and Aita, C.: Low temperature reactive sputter deposition of vanadium oxide. J. Vac. Sci. Technol. A 3, 660 (1985).Google Scholar
16Miyazaki, H., Utsuno, F., Shigesato, Y., and Yasui, I.: The structural characteristics of VOx films prepared by He-introduced reactive RF unbalanced magnetron sputtering. Thin Solid Films 281-282, 436 (1996).Google Scholar
17Kusano, E. and Theil, J.: Effects of microstructure and nonstoichiometry on electrical properties of vanadium dioxide films. J. Vac. Sci. Technol. A 7, 1314 (1989).CrossRefGoogle Scholar
18Chung, C., Wu, L., and Lee, S.: Fabrication of thin film vanadium oxide for microbolometer. Int. J. Nonlinear Sci. Numerical Sim. 3, 299 (2002).Google Scholar
19Jerominek, H., Picard, F., and Vincent, D.: Vanadium oxide films for optical switching and detection. Opt. Eng. 32, 2092 (1993).CrossRefGoogle Scholar
20Rata, A.D., Chezan, A.R., Haverkort, M.W., Hsieh, H.H., Lin, H.J., Chen, C.T., Tjeng, L.H., and Hibma, T.: Growth and properties of strained VOx thin films with controlled stoichiometry. Phys. Rev. B Condens. Matter 69, 075404 (2004).CrossRefGoogle Scholar
21Banus, M.D., Reed, T.B., and Strauss, A.J.: Electrical and magnetic properties of TiO and VO. Phys. Rev. B Condens. Matter 5, 2775 (1972).CrossRefGoogle Scholar
22Sellers, J.: Asymmetric bipolar pulsed DC: The enabling technology for reactive PVD. Surf. Coat. Technol. 98, 1245 (1998).CrossRefGoogle Scholar
23Doolittle, L.R.: Algorithms for the rapid simulation of Rutherford backscattering spectra. Nucl. Inst. Meth., Phys. Res. B 9, 344 (1985).CrossRefGoogle Scholar
24Stringer, J.: The vanadium-oxygen system—A review. J. Less Common Met. 8, 1 (1965).Google Scholar
25Goodenough, J.B.: Influence of atomic vacancies on the properties of transition-metal oxides. I. TiOx and VOx. Phys. Rev. B Condens. Matter 5, 2764 (1972).CrossRefGoogle Scholar
26Hebert, C., Willinger, M., Su, D., Pongratz, P., Schattschneider, P., and Schlogl, R.: Oxygen K-edge in vanadium oxides: Simulations and experiments. Eur. Phys. J. B 28, 407 (2002).CrossRefGoogle Scholar
27Willinger, M.: Investigation of the Oxygen K-Edge Fine Structure in Vanadium Oxides (Institut fur Angewandte une Technische Physik der Technischen Universitat Wien, Berlin, 2001), p. 65.Google Scholar
28Igasaki, Y. and Mitsuhashi, H.: Origin of negative temperature coefficient of resistivity in polycrystalline Ti-N films. J. Appl. Phys. 54, 836 (1983).Google Scholar
29Murawski, L., Chung, C., and Mackenzie, J.: Electrical properties of semiconducting oxide glasses. J. Non-Cryst. Solids 32, 91 (1979).CrossRefGoogle Scholar
30Szorenyi, T., Bali, K., and Hevesi, I.: Amorphous vanadium oxide by CVD: Preparation, electrical and magnetic properties. J. Phys. Coll. 42, 997 (1981).Google Scholar
31Baranovski, S.: Charge Transport in Disordered Solids, edited by Capper, P., Kasap, S., and Willoughby, A. (John Wiley & Sons, Chichester, 2006), p. 479.Google Scholar
32Mott, N.F.: Conduction in glasses containing transition metal ions. J. Non-Cryst. Solids 1, 1 (1968).CrossRefGoogle Scholar
33Meyer, W. and Neldel, H.: A relation between the energy constant e and the quantity constant a in the conductivity-temperature formula for oxide semiconductors. Z. Tech. Phys. 18, 588 (1937).Google Scholar
34Meiling, H. and Schropp, R.: The inverse Meyer-Neldel rule in thin-film transistors with intrinsic heterogeneous silicon. Appl. Phys. Lett. 74, 1012 (1999).Google Scholar
35Lucovsky, G. and Overhof, H.: An application of the statistical shift model to the inverted Meyer-Neldel, M-N, relationship in heavily-doped microcrystalline Si, uc-Si. J. Non-Cryst. Solids 164-166, 973 (1993).CrossRefGoogle Scholar