Abstract
Heating and annealing effects on the optical properties of slightly blue substoichiometric molybdenum trioxide thin films are reported partially. During heating and annealing, different levels of coloration seem to be generated by simultaneous reduction and proton injection into thin films, which cause the formation of hydrogen molybdenum bronzes of different concentrations. The optical band gap, Eo, of MoO3 thin film when annealed in between 313 and 473 K is decreased to 2.82 eV, and this reduction in Eo has been explained with a view to phonon and polaron species. Moreover, temperature-dependent change in the optical band gap has also been interpreted in terms of band gap slope, B, and the real part of the refractive index, n. Urbach slope, σ, also goes down to 0.67 eV−1 due to annealing treatment. Using the oscillator model, a phonon energy, hνo, of about 0.08 eV was found for the reported MoO3 thin film which is very close to the characteristic phonon energy of MoO3. Over and above, the intensity for the blue absorption band, over the photon energy range 0.4–3.0 eV, also reaches a maximum as MoO3 thin film is annealed at 473 K for 1 h and then decreases by 32% after annealing at the same temperature for 2 h. This phenomenon is due to polaronic band intensity which rises and falls during annealing. Half-width of the blue band, as found by fitting polaron model, is changed only by 3% on annealing the MoO3 thin film at 473 K as compared to its value at room temperature.
Similar content being viewed by others
References
Y.A. Yang, Y.W. Cao, B.H. Loo, and J.N. Yao, J. Phys. Chem. B 102, 9392 (1998).
Z.S. Guan, J.N. Yao, Y.A. Yang, and B.H. Loo, J. Electroanal. Chem. 443, 175 (1998).
D.A. Wruck and M. Rubin, J. Electrochem. Soc. 140, 1097 (1993).
L. Yiting, D. Wen, Z. Jinwei, and S. Xinqi, Axue Huaxue (Chinese) 11, 28 (1996).
A. Abdellaoui, L. Martin, and A. Donnadieu, Phys. Status Solidi A 109, 455 (1988).
J.S.E.M. Svesson and C.G. Granqvist, Proc. SPIE 502, 30 (1984).
M. Green, H.I. Evans, and Z. Hussain, 2nd International Symposium on Polymer Electrolytes, Sienna, 1989, edited by B. Scrosati (Elsevier, London, United Kingdom, 1990), p. 449.
A.M. Anderson, C.G. Granquvist, and J.R. Stevens, Appl. Opt. 28, 3295 (1989); SPIE 1016, 41 (1988).
M.S. Whittingham, Prog. Solid State Chem. 12, 41 (1978).
C. Julien, Mater. Sci. Eng. B 6, 9 (1991).
A.N. Dey, J. Electrochem. Soc. 120, 228C (1973); Electrochemical Society Extended Abstracts, Fall Meeting, Boston, MA, Oct. 7-11, 1973 (Electrochemical Society, Pennington, NJ, 1973), Abstract 54, p. 132.
L. Campanella and G. Pistoia, J. Electrochem. Soc. 118, 1905 (1971).
M.S. Whittingham, J. Electrochem. Soc. 122, 713 (1975).
V.A. Ioffe, I.B. Patrina, and E.V. Zelenetskaya, Phys. Status Solidi 37, 425 (1970).
N. Koshida, K. Ohtaka, M. Ando, M. Komuro, and N. Atoda, Jpn. J. Appl. Phys., Part I 29, 2299 (1990).
M. Hashimoto, S. Watanuki, N. Koshida, M. Komuro, and N. Atoda, Jpn. J. Appl. Phys., Part I 35, 3665 (1996).
N. Koshida, K. Ichinose, K. Ohtaka, M. Komuro, and N. Atoda, J. Vac. Sci. Technol. B 8, 1093 (1990).
N. Koshida, K. Yoshida, S. Watanuki, M. Komuro, and N. Atoda, Jpn. J. Appl. Phys., Part I 30, 3246 (1991).
N. Koshida, S. Watanuki, K. Yoshida, K. Endo, M. Komuro, and N. Atoda, Jpn. J. Appl. Phys., Part I 31, 4483 (1992).
M.R. Tubbs, Phys. Status Solidi A 21, 253 (1974).
F.G.K. Baucke and J.A. Duffy, Chem. Br. 21, 643 (1985).
C.G. Granqvist, Solid State Ionics 53-56, 479 (1992).
A.I. Gavrilyak, A.A. Mansurov, and F.A. Chudnovskii, Sov. Tech. Phys. Lett. 1016, 292 (1984); see also A.I. Gavrilyak, T.G. Lanskaya, and F.A. Chudnovskii, Sov. Phys. Tech. Phys. 32, 964 (1987).
G. Travaglini, P. Wachter, J. Marcus, and C. Schlenker, Solid State Commun. 37, 599 (1981); Solid State Commun. 42, 407 (1982).
G. Travaglini and P. Wachter, Solid State Commun. 47, 217 (1983).
M. Greenblatt, K.V. Ramanujachary, W.H. McCarroll, R. Neifeld, and J.V. Waszczak, Solid State Chem. 59, 149 (1985).
W.B. Jackson, N.M. Johnson, and D.K. Biegelsen, Appl. Phys. Lett. 43, 195 (1983).
V. Wittwer, O.F. Schirmer, and P. Schlotter, Solid State Com-mun. 25, 977 (1978).
B.K. Chakraverty, J. Phys. 42, 1351 (1981).
P.A. Gillet, J.L. Fourquet, and O. Bohnke, Mater. Res. Bull. 27, 1145 (1992).
Z. Hussain, Ph.D. Thesis, University of London, London, United Kingdom (2000).
H.I. Evans, Ph.D. Thesis, University of London, London, United Kingdom (1987).
O. Bohnke and G. Robert, Solid State Ionics 6, 115 (1982).
N. Miyata and S. Akiyashi, J. Appl. Phys. 58, 1651 (1985).
M.A. Osman, A. Othman, and M.A. Abd-Alla, J. Phys. D: Appl. Phys. 24, 1203 (1991).
S.K. Deb and J.A. Chopoorian, J. Appl. Phys. 37, 4818 (1966).
Y. Hiruta, M. Kitao, and S. Yamada, Jpn. J. Appl. Phys. 23, 1624 (1984).
K.H. Hellwege and A.M. Hellwege, Landolt-Bornstein III (Springer Verlag, Berlin, Germany, 1975), Vol. 7, pp. 488 and 496.
G. Hagg and A. Magneli, Rev. Pure Appl. Chem. 4, 235 (1954).
D.L. Neirk, J.C. Fagerli, M.L. Smith, D. Mosman, and T.C. De Vore, J. Mol. Struct. 244, 165 (1991).
M. Green and Z. Hussain, J. Appl. Phys. 69, 7788 (1991).
J.M. Bennett and M.J. Booty, Appl. Opt. 5, 41 (1966); F. Abeles, in Optical Properties of Solids, edited by F. Abeles (North-Holland, Amsterdam, The Netherlands, 1972), p. 93.
T.M. Donovan, W.E. Spicer, J.M. Bennett, and E.J. Ashley, Phys. Rev. B2, 397 (1970); F. Abeles, Progress in Optics, edited by E. Wolf (Wiley, New York, 1963), Vol II, p. 268.
H.E. Bennett and J.M. Bennett, in Physics of Thin Films, edited by G. Hass and R.E. Thun (Academic Press, New York, 1967), Vol 4, p. 12.
Ohba, Shun-Ichi Ikawa, and Shun-Ichi, J. Appl. Phys. 64, 4141 (1988).
D.L. Wood and T. Tauc, Phys. Rev. B 5, 3144 (1972).
M. Anwar and C.A. Hogarth, Phys. Status Solidi A 109, 469 (1988).
S.K. Deb, Proc. R. Soc. A 304, 211 (1968).
M.S. Jagadeesh and V. Damodara Das, J. Non-Cryst. Solids 28, 327 (1978).
A. Madan and M. Shaw, The Physics and Applications of Amorphous Semiconductors (Academic Press, New York, 1988).
J. Tauc, in Optical Properties of Solids, edited by F.A. Abeles (North-Holland, Amsterdam, The Netherlands, 1971).
G.S. Nadkarni and J.G. Simmons, J. Appl. Phys. 43, 3741 (1972).
L. Kihlborg, Ark. Kemi 21, 443 (1963).
P.G. Dickens and D.J. Neild, Trans. Faraday Soc. 64, 13 (1968).
O. Bohnke, G. Frand, M. Fromm, J. Weber, and O. Greim, Appl. Surf. Sci. 93, 45 (1996)
S.K. Deb, Philos. Mag. 27, 801 (1973).
B.A. Anderson, Y. Kim, D.W. Ewing, R.K. Grasselli, and M. Tenhover, Surf. Sci. 134, 237 (1983).
G.M. Ramans, J.V. Gabrusenoks, A.R. Lusis, and A.A. Patmalnieks, J. Non-Cryst. Solids 90, 637 (1987); Phys. Status Solidi 74, K41 (1982).
P.K. Gupta and K.L. Chopra, Appl. Phys. Lett. 51, 1527 (1987); see also J. Appl. Phys. 62, 4273 (1987).
G. Hollinger, T.M. Duc, and A. Deneuville, Phys. Rev. Lett. 37, 1564 (1976).
L. Su and Z. Lu, J. Phys. Chem. Solids 59, 1175 (1998).
L. Su, L. Zhang, J. Fang, M. Xu, and Z. Lu, Sol. Energy Mater. Sol. Cells 58, 133 (1999).
B. Gerand, G. Nowogrocki, J. Guenot, and M. Figlarz, J. Solid State Chem. 29, 429 (1979).
B. Gerand, G. Nowogrocki, and M. Figlarz, J. Solid State Chem. 38, 312 (1981).
O.F. Schirmer, J. Phys., Colloq. 6, 479 (1980).
E. Iguchi and K. Akashi, Jpn. J. Phys. Soc. 61, 3385 (1992).
G. Anderson and A. Magneli, Acta. Chem. Scand. 4, 793 (1950); see also G. Anderson, Acta Chem. Scand. 7, 154 (1953).
E.M. McCarron, III, J. Chem. Soc., Chem. Commun. 198, 336 (1986).
H.Z. Braekken, Kristallografiya 78, 484 (1931).
Y. Shigesato, A. Murayama, T. Kamimori, and K. Matsuhiro, Appl. Surf. 33/34, 804 (1988).
V.B. Krebs, Acta Crystallogr. B 28, 2222 (1972).
O. Glemser and G. Lutz, Z. Anorg. Allg. Chem. 264, 17 (1951).
O. Glemser, G. Lutz, and G. Meyer, Z. Anorg. Allg. Chem. 285, 173 (1956).
C. Ritter, W. Muller-Warmuth, and R. Schollhorn, J. Chem. Phys. 83, 6130 (1985).
F. Endres and G. Schwitzgebel, Electrochim. Acta 43, 431 (1998).
A.I. Gavrilyuk, N.M. Reinov, and F.A. Chudnovskii, Sov. Tech. Phy. Lett. 5, 514 (1979); see also Sov. Tech. Phys. Lett. 20, 295 (1994).
A. Guerfi, R.W. Paynter, and Le H. Dao, J. Electrochem. Soc. 142, 3457 (1995).
L. Kihlborg and A. Magneli, Acta Chem. Scand. 9, 471 (1955).
Y. Shigesato, Jpn. J. Appl. Phys. 30, 145 (1991).
P.F. Carcia and E.M. McCarron, III, Thin Solid Films 155, 53 (1987).
M. Shiojiri, T. Miyano, and C. Kaito, Jpn. J. Appl. Phys. 18, 1937 (1979); Jpn. J. Appl. Phys. 17, 567 (1978).
J. Purans, A. Kuzmin, A. Balerna, E. Bernieri, and E. Burattini, Proceedings of the 2nd European Conference on Progress in X-ray Synchrotron Radiation Research, Rome, 1989 (Ital. Phys. Soc., Bologna, Italy, 1990), Vol. 25, p. 679.
A. Balerna, E. Bernieri, E. Burattini, A. Kuzmin, A. Lusis, J. Purans, and P. Cikmach, Nucl. Instrum. Methods Phys. Res. A 308, 234 (1991).
J.V. Gabrusenoks, P.D. Chikmach, A.R. Lusis, J.J. Kleperis, and G.M. Ramans, Solid State Ionics 14, 25 (1984).
F. Bonino, L. Peraldo Bicelli, B. Rivolta, M. Lazzari, and F. Festorazzi, Solid State Ionics 17, 21 (1985).
J.T. Szymanski and A.C. Roberts, Can. Mineral. 22, 681 (1984).
J.R. Gunter, J. Solid State Chem. 5, 354 (1972).
J.S.E.M. Svensson, D.K. Benson, and C.E. Tracy, SPIE 1016, 19 (1988).
F. Harb, B. Gerand, G. Nowogrocki, and M. Figlarz, Solid State Ionic 32/33, 84 (1989).
O. Bertrand, N. Floquet, and D. Jacquot, Surf. Sci. 164, 305 (1985).
P.K. Shen, J. Syed-Bokhari, and A.C.C. Tseung, J. Electrochem. Soc. 138, 2778 (1991); J. Mater. Chem. 2, 1141 (1992).
C. Julien, L. El-Farh, M. Balkanski, O. Md. Hussain, and G.A. Nazri, Appl. Surf. Sci. 65/66, 325 (1993).
V.K. Sabhapathi, O. Md. Hussain, P.S. Reddy, K.T.R. Reddy, S. Uthana, B.S. Naidu, and P.J. Reddy, Phys. Status Solidi A 148, 167 (1995).
T. Hirata, Appl. Surf. Sci. 40, 179 (1989).
F. Kumada, M. Okamoto, M. Baba, and T. Ikeda, Jpn. J. Appl. Phys. 25, L574 (1986).
E.W. Serwicka, Crit. Rev. Surf. Chem. 1, 27 (1990).
A. Magneli, Acta Crystallogr. 6, 495 (1953).
R. Juryska, Phys. Status Solidi A 72, K161 (1975).
L.E. Firment and A. Ferretti, Surf. Sci. 129, 155 (1983); also see V.E. Henrich, Rep. Prog. Phys. 48, 1481 (1985).
D. Tinet, P. Canesson, H. Estrade, and J.J. Fripiat, J. Phys. Chem. Solids 41. 583 (1979).
P. Pichat, M-N. Mozzanega, and C. Hoang-Van, J. Phys. Chem. 92, 467 (1988).
R. Erre, M.H. Legay, and J.J. Fripiat, Surf. Sci. 127, 69 (1983).
J.W. Rabalais, R.J. Colton, and A.M. Guzman, Chem. Phys. Lett. 29, 131 (1974).
M. Rothschild and A.R. Forte, Appl. Phys. Lett. 59, 1790 (1991).
Electronic Processes in Non-Crystalline Materials, edited by N.F. Mott and E.A. Davis (Oxford University, Oxford, United Kingdom, 1979), p. 272.
S.K. Deb, Sol. Energy Mater. Sol. Cells 39, 191 (1995).
A. Nakamura, K. Nakada, Y. Ito, and E. Koishi, J. Appl. Phys. 57, 135 (1985).
E.A. Davis and N.F. Mott, Philos. Mag. 22, 903 (1970).
B.W. Faughnan and R.S. Crandall, in Display Devices, edited by J.I. Pankove, Topics in Applied Physics (Springer-Verlag, Berlin, Heidelberg, Germany, 1980), Vol. 40, p. 181.
L. Tichy, E. Sleeckx, P. Nagels, and H. Ticha, Philos. Mag. B 73, 213 (1996).
G.D. Cody, T. Tiedje, B. Abeles, B. Brooks, and Y. Goldstein, Phys. Rev. Lett. 47, 1480 (1981); G.D. Cody, in Semiconductors and Semimetals, edited by J.I. Pankove (Academic, New York, 1984), Vol. 21, Part B.
J.I. Pankove, Phys. Rev. 140, A2059 (1965).
D. Redfield and M.A. Afromowitz, Appl. Phys. Lett. 11, 138 (1967).
S. John and C.H. Grein, Rev. Solid State Sci. 4, 1 (1990).
J. Lipavicius, E. Cijauskas, and A. Audzijonis, Phys. Status Solidi A 148, K97 (1988).
F.A. Shroder, Acta Crystallogr. B 31, 2294 (1975).
T. Skettrup, Phys. Rev. B 18, 2622 (1978).
T. He, P. Ehrhart, and P. Meuffels, J. Appl. Phys. 79, 3219 (1996).
A. Sumi and Y. Toyozawa, J. Phys. Soc. Jpn. 31, 342 (1971); 55, 137 (1973).
G.A. Medvedkin, Y.V. Rud, and M.A. Tairov, Phys. Status Solidi B 144, 809 (1987).
T. Shioda, S. Chichibu, T. Irie, and H. Nakanishi, J. Appl. Phys. 80, 1106 (1996).
M.V. Kurik, Phys. Status Solidi A 8, 9 (1971).
D.I. Desnica, M. Kranjcec, and B. Celustka, J. Phys. Chem. Solids 52, 915 (1991).
H. Mahr, Phys. Rev. 125, 1510 (1962).
D. Emin, Phys. Rev. B 48, 13691 (1993).
T.H. Fleisch and G.J. Mains, J. Chem. Phys. 76, 780 (1982).
A.W. Faughnan, R.S. Crandall, and P.M. Heyman, RCA Rev. 36, 177 (1975).
J.M. Berak and M.J. Sienko, J. Solid State Chem. 2, 109 (1970).
T. Masumi, Prog. Theor. Phys. Suppl. 22, 57 (1975).
E. Salje and B. Guttler, Philos. Mag. B 50, 607 (1984).
H. Demiryont and S.C. Schulz, SPIE 1149, 28 (1989).
J.B. Goodenough, in Progress in Solid State Chemistry, edited by H. Reiss (Pergamon, London, United Kingdom, 1971), Vol. 5, p. 145.
G.S. Nadkarni and J.G. Simmons, J. Appl. Phys. 41, 545 (1970); see also J. Appl. Phys. 43, 3741 (1972).
J.G. Zhang, C.E. Tracy, D.K. Benson, and S.K. Deb, J. Mater. Res. 8, 2649 (1993); see also SPIE 2017, 104 (1993).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Hussain, Z. Optical and electrochromic properties of heated and annealed MoO3 thin films. Journal of Materials Research 16, 2695–2708 (2001). https://doi.org/10.1557/JMR.2001.0369
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1557/JMR.2001.0369