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The phase transition temperature of vanadium dioxide (VO2) thin films shifts to the vicinity of room temperature by reducing the dimensions from microscale to nanoscale without the use of any dopant. This quantum size effect elucidated by studying the structural, optical and electrical properties of nanothin and microthin films of VO2 across their semiconductor–metal phase transitions has been demonstrated in this reported work. The films fabricated on glass substrates via the inorganic sol–gel route were characterised by Rutherford backscattering spectrometry (RBS), X-ray diffractometery, scanning electron microscopy, ultraviolet–visible spectroscopy and the four-probe method. The RBS results estimate a layer thickness of 15 and 291 nm for nanothin and microthin films, respectively. The films were polycrystalline in their nature of [011] orientation with regular and irregular crystallites of a cuboidal surface morphology. Estimation of crystallite size revealed that nanothin films attain poor crystallinity as compared with microthin films. The blue shift was observed in nanothin films from microthin films as maximum absorption occurred at wavelengths of 360 and 443 nm, respectively. Optical bandgaps of 2.3 and 1.87 eV were found for nanothin and microthin films, respectively. Depletion in metal-to-semiconductor and semiconductor-to-metal transition temperatures were experienced from higher temperature regimes of 341 and 335 K for microthin films to lower temperature regimes of 319 and 305 K for nanothin films, respectively.
References
-
-
1)
-
25. Dai, J., Wang, X., He, S., Huang, Y., Yi, X.: ‘Low temperature fabrication of VOx thin films for uncooled IR detectors by direct current reactive magnetron sputtering method’, Infrared Phys. Technol., 2008, 51, p. 287 (doi: 10.1016/j.infrared.2007.12.002).
-
2)
-
28. Outkina, E.A., Vorobyova, A.I., Khodin, A.A.: ‘Formation and properties of thin-film composites vanadium oxide/porous anodic aluminum oxide’, Russ. Microelectron., 2010, 39, p. 273 (doi: 10.1134/S1063739710040050).
-
3)
-
38. Liebsch, A., Ishida, H., Bihlmayer, G.: ‘Coulomb correlations and orbital polarization in the metal-insulator transition of VO2’, Phys. Rev. B, 2005, 71, p. 085109 (doi: 10.1103/PhysRevB.71.085109).
-
4)
-
6. Barker, A.S., Verleur, H.W., Guggenheim, H.J.: ‘Infrared optical properties of vanadium dioxide above and below transition temperature’, Phys. Rev. Lett., 1966, 17, p. 1286 (doi: 10.1103/PhysRevLett.17.1286).
-
5)
-
14. Zhang, Y., Zhang, J., Zhang, X., Huang, C., Zhong, Y., Deng, Y.: ‘The additives W, Mo, Sn and Fe for promoting the formation of VO2 (M) and its optical switching properties’, Mater. Lett., 2013, 92, p. 61 (doi: 10.1016/j.matlet.2012.10.054).
-
6)
-
9. Karimov, K.S., Tahir, M.M., Saleem, M., Chani, M.T.S., Niaz, A.K.: ‘Temperature sensor based on composite film of vanadium complex (VO2(3-fl)) and CNT’, J. Semicond., 2015, 36.
-
7)
-
31. Nag, J., Haglund, R.F.: ‘Synthesis of vanadium dioxide thin films and nanoparticles’, Phys. Condens. Matter, 2008, 20, p. 1 (doi: 10.1088/0953-8984/20/26/264016).
-
8)
-
26. Wang, N., Magdassi, S., Mandler, D., Long, Y.: ‘Simple sol–gel process and one-step annealing of vanadium dioxide thin films: synthesis and thermochromic properties’, Thin Solid Films, 2013, 534, p. 594 (doi: 10.1016/j.tsf.2013.01.074).
-
9)
-
29. Xu, M., Wang, J., Li, L., Wu, C., Zhao, Y., Zuo, H.: ‘Preparation of thermochromic vanadium dioxide thin films by pulsed-magnetron sputtering’, Appl. Mech. Mater., 2013, 377, p. 227 (doi: 10.4028/www.scientific.net/AMM.377.227).
-
10)
-
23. Warwick, M.E., Ridley, I., Binions, R.: ‘The effect of variation in the transition hysteresis width and gradient in thermochromic glazing systems’, Sol. Energy Mater. Sol. Cells, 2015, 140, p. 253 (doi: 10.1016/j.solmat.2015.04.022).
-
11)
-
13. Lu, Y., Zhou, S., Gu, G., Wu, L.: ‘Preparation of transparent, hard thermochromic polysiloxane/tungsten-doped vanadium dioxide nanocomposite coatings at ambient temperature’, Thin Solid Films, 2013, 534, p. 231 (doi: 10.1016/j.tsf.2013.02.130).
-
12)
-
12. Paone, A., Joly, M., Sanjines, R., Romanyuk, A., Scartezzini, J.L., Schüler, A.: ‘Thermochromic films of VO2:W for smart solar energy applications’. SPIE Solar Energy Technology, 2009, pp. 74100F–74100F.
-
13)
-
17. Mlyuka, N., Niklasson, G., Granqvist, C.G.: ‘Mg doping of thermochromic VO2 films enhances the optical transmittance and decreases the metal–insulator transition temperature’, Appl. Phys. Lett., 2009, 95, p. 171909 (doi: 10.1063/1.3229949).
-
14)
-
36. Ghobad, N.: ‘Band gap determination using absorption spectrum fitting procedure’, Int. Nano Lett., 2013, 3, p. 2 (doi: 10.1186/2228-5326-3-2).
-
15)
-
18. Li, S.Y., Mlyuka, N.R., Primetzhofer, D., et al: ‘Bandgap widening in thermochromic Mg-doped VO2 thin films: quantitative data based on optical absorption’, Appl. Phys. Lett., 2013, 103, p. 161907 (doi: 10.1063/1.4826444).
-
16)
-
3. Goodenough, J.B.: ‘The two components of the crystallographic transition in VO2’, Solid State Chem., 1971, 3, p. 490 (doi: 10.1016/0022-4596(71)90091-0).
-
17)
-
30. Chae, B.G., Youn, D.H., Kim, H.T., Maeng, S.Y., Kang, K.Y.: ‘Fabrication and electrical properties of pure VO2 phase films’, 2003, .
-
18)
-
33. Khan, G.R., Khan, R.A.: ‘Ergonomic synthesis suitable for industrial production of silver-festooned zinc oxide nanorods’, Int. J. Nanosci., 2015, .
-
19)
-
35. Caruthers, E., Kleinman, L.: ‘Energy bands of semiconducting VO2’, Phys. Rev. B, 1973, 7, p. 3760 (doi: 10.1103/PhysRevB.7.3760).
-
20)
-
43. Eyert, V.: ‘VO2: a novel view from band theory’, Phys. Rev. Lett., 2011, 107, p. 016401 (doi: 10.1103/PhysRevLett.107.016401).
-
21)
-
19. Shen, N., Chen, S., Chen, Z., et al: ‘The synthesis and performance of Zr-doped and W–Zr-codoped VO2 nanoparticles and derived flexible foils’, J. Mater. Chem. A, 2014, 2, p. 15087 (doi: 10.1039/C4TA02880E).
-
22)
-
27. Warwick, M.E., Binions, R.: ‘Chemical vapour deposition of thermochromic vanadium dioxide thin films for energy efficient glazing’, J. Solid State Chem., 2014, 214, p. 53 (doi: 10.1016/j.jssc.2013.10.040).
-
23)
-
34. Kürüm, U., Yaglioglu, H.G., Küçüköz, B., et al: ‘Excited state dynamics of nanocrystalline VO2 with white light continuum time resolved spectroscopy’, Opt. Commun., 2014, 333, p. 109 (doi: 10.1016/j.optcom.2014.07.064).
-
24)
-
32. Vinichenko, D.A., Zlomanov, V.P., Vasil'ev, V.A., Seregin, D.S., Berezina, O.Y.: ‘Synthesis of vanadium dioxide films by a modified sol–gel process’, Inorg. Mater., 2011, 47, p. 279 (doi: 10.1134/S0020168511030216).
-
25)
-
41. Qazilbash, M.M., Burch, K.S., Whisler, D., et al: ‘Correlated metallic state of vanadium dioxide’, Phys. Rev. B, 2006, 74, p. 205118 (doi: 10.1103/PhysRevB.74.205118).
-
26)
-
45. Narayan, J., Bhosle, V.M.P.: ‘Phase transition and critical issues in structure–property correlations of vanadium oxide’, Appl. Phys., 2006, 100, p. 103524 (doi: 10.1063/1.2384798).
-
27)
-
20. Ramírez, J.G., Sharoni, A., Dubi, Y., Gomez, M.E., Schuller, I.K.: ‘First-order reversal curve measurements of the metal-insulator transition in VO2: signatures of persistent metallic domains’, Phys. Rev., 2009, B79, p. 235110 (doi: 10.1103/PhysRevB.79.235110).
-
28)
-
15. Liu, S.J., Fang, H.W., Su, Y.T., Hsieh, J.H.: ‘Metal–insulator transition characteristics of Mo- and Mn-doped VO2 films fabricated by magnetron cosputtering technique’, Jpn. J. Appl. Phys., 2014, 53, p. 063201 (doi: 10.7567/JJAP.53.063201).
-
29)
-
39. Biermann, S., Poteryaev, A., Lichtenstein, A.I., Georges, A.: ‘Dynamical singlets and correlation-assisted Peierls transition in VO2’, Phys. Rev. Lett., 2005, 94, p. 026404 (doi: 10.1103/PhysRevLett.94.026404).
-
30)
-
2. Hong, W.K., Cha, S.N., Sohn, J.I., Kim, J.M.: ‘Metal-insulator phase transition in quasi-one-dimensional VO2 structures’, J. Nanomaterials, 2015, 501, p. 538954.
-
31)
-
11. Jiang, L., Carr, W.N.: ‘Design, fabrication and testing of a micromachined thermo-optical light modulator based on a vanadium dioxide array’, J. Micromech. Microeng., 2004, 14, p. 833 (doi: 10.1088/0960-1317/14/7/001).
-
32)
-
16. Batista, C., Ribeiro, R.M., Teixeira, V.: ‘Synthesis and characterization of VO2-based thermochromic thin films for energy-efficient windows’, Nanoscale Res. Lett., 2011, 6, p. 1 (doi: 10.1186/1556-276X-6-301).
-
33)
-
1. Warwick, M.E., Binions, R.: ‘Advances in thermochromic vanadium dioxide films’, J. Mater. Chem. A, 2014, 2, p. 3275 (doi: 10.1039/C3TA14124A).
-
34)
-
40. Haverkort, M.W., Hu, Z., Tanaka, A., et al: ‘Orbital-assisted metal-insulator transition in VO2’, Phys. Rev. Lett., 2005, 95, p. 196404 (doi: 10.1103/PhysRevLett.95.196404).
-
35)
-
8. Li, W., Ji, S., Qian, K., Jin, P.: ‘Preparation and characterization of VO2(M)-SnO2 thermochromic films for application as energy-saving smart coatings’, J. Colloid Interface Sci., 2015, 456, p. 166 (doi: 10.1016/j.jcis.2015.06.013).
-
36)
-
42. Wei, J., Wang, Z., Chen, W., Cobden, H.: ‘New aspects of the metal–insulator transition in single-domain vanadium dioxide nanobeams’, Nat. Nanotechnol., 2009, 4, p. 420 (doi: 10.1038/nnano.2009.141).
-
37)
-
5. Case, F.C.: ‘Influence of ion beam parameters on the electrical and optical properties of ion-assisted reactively evaporated vanadium dioxide thin films’, Vac. Sci. Technol., 1987, A5, p. 1762 (doi: 10.1116/1.574534).
-
38)
-
44. Wang, C.X., Yang, G.W.: ‘Thermodynamics of metastable phase nucleation at the nanoscale’, Mater. Sci. Eng. R, 2005, 49, p. 157 (doi: 10.1016/j.mser.2005.06.002).
-
39)
-
24. Lopez, R., Boatner, L.A., Haynes, T.E.: ‘Enhanced hysteresis in the semiconductor-to-metal phase transition of VO2 precipitates formed in SiO2 by ion implantation’, Appl. Phys. Lett., 2001, 79, p. 3161 (doi: 10.1063/1.1415768).
-
40)
-
22. Nishikawa, M., Nakajima, T., Kumagai, T., Okutani, T., Tsuchiya, T.: ‘Adjustment of thermal hysteresis in epitaxial VO2 films by doping metal ions’, J. Ceram. Soc. Jpn, 2011, 119, p. 577 (doi: 10.2109/jcersj2.119.577).
-
41)
-
21. Zhang, Y., Huang, W.X., Shi, Q.W., Song, L.W., Xu, Y.J.: ‘Thermal modulation behavior inside the hysteresis loop of W–Mo co-doping vanadium dioxide film’, J. Inorg. Mater., 2013, 28, p. 497 (doi: 10.3724/SP.J.1077.2013.12358).
-
42)
-
7. Li, Y., Ji, S., Gao, Y., Luo, H., Kanehira, M.: ‘Core-shell VO2@ TiO2 nanorods that combine thermochromic and photocatalytic properties for application as energy-saving smart coatings’, , 2013, vol. 3.
-
43)
-
10. Jiang, L., Carr, W.N.: ‘Vanadium dioxide thin films for thermo-optical switching applications’. MRS Proc., 2003, vol. 785.
-
44)
-
37. Wentzcovitch, R.M., Schulz, W.W., Allen, P.B.: ‘VO2: Peierls or Mott-Hubbard? A view from band theory’, Phys. Rev. Lett., 1994, 72, p. 3389 (doi: 10.1103/PhysRevLett.72.3389).
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