Abstract
Optical band gaps, Urbach inverse slopes, and coloration bands of various samples of annealed, microcrystalline LixMoO3-bronze thin films in the concentration range 0<x<0.6 were determined over the photon energy range from 0.4 eV to 4.2 eV. On investigation, it is learned that the measured, optical band gaps do not shift rigidly over the annealing temperature range 293≤T≤423 K and, therefore, do not reveal the Burstein-Moss effect or reflect any stable, crystallographic phase transformation during any investigated annealing cycle. A model relating the temperature-dependent optical gap to the real part of the refractive index has also been developed, and this model fits very well to the annealed data within a maximum error of about 20%. Next, using an oscillator model, a phonon energy of ∼0.08 eV was obtained, which is very close to the characteristic phonon energy of the material, MoO3. Using this model, it becomes more certain that the contributions to the Urbach absorption edge for the annealed-molybdenum bronzes are coming from the structural and compositional disorder. In another finding, it was found that the absorption-peak energy for the annealed data was about 1.5–1.6 eV, which is still broad and asymmetrical, and therefore, it is almost of the Mo6+ (or Mo4+)-Mo5+ intervalence or polaronic type. Using the polaron model, the half-bandwidth of the coloration bands of investigated, annealed LixMoO3-thin films was found to be almost constant, which is consistent with the nonrigid band behavior.
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References
T. Toyoda, J. Appl. Phys. 63, 5166 (1988).
J. Magai, T. Kamimori, and M. Mizuhashi, SPIE 502, 59 (1984).
M. Green, H.I. Evans, Z. Hussain, 2nd Int. Symp. Polymer Electrolytes, ed. B. Scrosati (London: Elsevier, 1990), pp. 449–459.
A. Abdellaoui, L. Martin, and A. Donnadieu, Phys. Status Solidi (a) 109, 455 (1988).
M. Nagasu and N. Koshida, J. Appl. Phys. 71, 398 (1992).
S.K. Deb, Sol. Energy Mater. Sol. Cells 25, 327 (1992).
M.R. Tubbs, Phys. Status Solidi (a) 21, 253 (1974).
S.K. Deb and J.A. Chopoorian, J. Appl. Phys. 37, 4818 (1966).
J.G. Choi, R.L. Curl, and L.T. Thompson, J. Catal. 218, 146 (1994); see also J.G. Choi and L.T. Thompson, Appl. Surf. Sci. 93, 143 (1996).
A.I. Gavrilyuk, N.M. Reinov, and F.A. Chudnovskii, Sov. Tech. Phys. Lett. 5, (1979); and Sov. Tech. Phys. Lett. 6, 512 (1980).
C. Julien, L. El-Farh, M. Balkanski, O.M. Hussain, and G.A. Nazri, Appl. Surf. Sci. 65/66, 325 (1993).
M.S. Whittingham, Prog. Solid State Chem. 12, 41 (1978); and J. Electrochem. Soc. 123, 315 (1976).
F. Benkhelife, P.V. Ashrit, G. Bader, F.E. Girouard, and V.-V. Truong, J. Appl. Phys. 74, 4691 (1993).
F. Bonio, L.P. Bicelli, B. Rivolta, M. Lazzari, and F. Festarazzi, Solid State Ionics 17, 21 (1985).
V. Wittwer, O.F. Schirmer, and P. Schlotter, Solid State Commun. 25, 977 (1978).
B.K. Chakraverty, J. Phys. 42, 1351 (1981).
A. Guerfi, R.W. Paynter, and L.H. Dao, J. Electrochem. Soc. 142, 3457 (1995).
N.S. McIntyre, D.D. Johonston, L.L. Coatsworth, R.D. Davidson, and J.R. Brown, Surf. Interface Anal. 15, 265 (1990).
M. Anwar, C.A. Hogarth, and R. Bulpett, J. Mater. Sci. 24, 3087 (1989).
J. Zhang, C.E. Tracy, D.K. Bension, and S.K. Deb, J. Mater. Res. 8, 80 (1993).
C. Bechinger, M.S. Burdis, and J.G. Zhang, Solid State Commun. 101, 753 (1997).
Z. Hussain (Ph.D. Thesis, University of London, 2001).
M. Green and Z. Hussain, J. Appl. Phys. 74, 3451 (1993).
H.I. Evans (Ph.D. Thesis, University of London, 1987).
J.W. Rabalais, R.J. Colton, and A.M. Guzman, Chem. Phys. Lett. 29, 131 (1974).
L. Kihlborg and A. Magneli, Acta Chem. Scand. 9, 471 (1955).
Y. Shigesato, A. Murayama, T. Kamimori, and K. Matsuhiro, Appl. Surf. Sci. 33/34, 804 (1988); and Y. Shigesato, Jpn. J. Appl. Phys. 30, 145 (1991).
J.V. Gabrusenoks, P.D. Chikmach, A.R. Lusis, J.J. Kleperis, and G.M. Ramans, Solid State Ionics 14, 25 (1984).
V.I. Kukuyev, E.A. Tutov, E.P. Domashevskaya, M.I. Yanovskaya, I.E. Obvintseva, and Y.N. Venevtsev, Sov. Phys. Tech. Phys. 32, 1176 (1987).
D.J. De Smet and J.L. Ord, Electrochem. Soc. 130, 280 (1983); see also D.J. De Smet, Electrochem. Acta 21, 1137 (1976).
D.J. De Smet and J.L. Ord, J. Electrochem. Soc. 134, 1734 (1987).
M. Green and Z. Hussain, J. Appl. Phys. 69, 7788 (1991).
T. Ohka and S.-I. Ikawa, J. Appl. Phys. 64, 4141 (1988).
J.R. Bellinghan, W.A. Phillips, and C.J. Adkins, J. Phys. Condens. Mater. 2, 6207 (1990).
J. Tauc, R. Grigorovici, and A. Vancu, Phys. Status Solidi 15, 627 (1966).
R. Swan, A.K. Ray, and C.A. Hogarth, Phys. Status Solidi (a) 127, 555 (1991).
T.S. Moss, Optical Properties of Semiconductors (London: Butterworth, 1973).
G.S. Nadkarni and J.G. Simmons, J. Appl. Phys. 41, 545 (1970); and J. Appl. Phys. 43, 3741 (1972).
D.L. Wood and J. Tauc, Phys. Rev. B5, 3144 (1972).
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. Denichelis, G. Kaniadakis, R. Spagnolo, and E. Tresso, Philos. Mag. B60, 713 (1989).
S. John and C. Soukoulis, Phys. Rev. Lett. 57, 1777 (1986).
H.W. Martienssen, J. Phys. Chem. Solids 2, 257 (1957).
M. Anwar and C.A. Hogarth, Phys. Status Solidi (a) 109, 469 (1988).
O.F. Schirmer, V. Wittwer, G. Baur, and G. Brandt, J. Electrochem. Soc. 124, 749 (1977); and O.F. Schirmer, J. Phys. (Paris) 6, 479 (1980).
P.D. Cikmach, J.J. Kleperis, A.R. Lusis, and G.M. Ramans, Phys. Status Solidi (a) 90, K1 (1985).
S.-H. Lee, H.M. Cheong, C.E. Tracy, A. Mascarenhas, D.K. Benson, and S.K. Deb, Electrochimica Acta 44, 3111 (1999).
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).
S. Badilescu, K. Boufker, P.V. Ashrit, and V.V. Truong, Proc. Soc. Photo. Opt. Instrum. Eng. 1401, 119 (1990); see also J. Electrochem. Soc. 136, 3599 (1989).
P.K. Shen, J. Syed-Bokhari, and A.C.C. Tseung, J. Electrochem. Soc. 138, 2778 (1991); see also P.K. Shen and A.C.C. Tseung, J. Mater. Chem. 2, 1141 (1992).
P.F. Carcia and E.M. Mc Carron III, Thin Solid Films 155, 53 (1987).
T. Hirata, Appl. Surf. Sci. 40, 179 (1989).
J.B. Parise, E.M. McCarron III, and A.W. Sleight, Mater. Res. Bull. 22, 803 (1987).
M. Shiojiri, T. Miyano, and C. Kaito, Jpn. J. Appl. Phys. 18, 1937 (1979); and Jpn. J. Appl. Phys. 17, 567 (1978).
J. Purans, A. Kuzmin, A. Balerna, E. Bernieri, and E. Burattini, Proc. 2nd. Europ. Conf. on Progress in X-ray Synchrotron Radiation Research (Bologna, Italy: Ital. Phys. Soc., 1990), p. 679.
A. Balerna, E. Bernieri, E. Burattini, A. Kuzmin, A. Lusis, J. Purans, and P. Cikmach, Nucl. Instrum. Methods Phys. Res. A308, 234 (1991).
N. Miyata and S. Akiyoshi, J. Appl. Phys. 58, 1651 (1985).
P.G. Dickens and G.J. Reynolds, Solid State Ionics 5, 331 (1981).
T.A. Bither, J.L. Gillson, and H.J. Young, Inorg. Chem. 5, 1559 (1966).
A.K. Ganguli, L. Ganapathi, J. Gopalakrishnan, and C.N.R. Rao, J. Solid State Chem. 74, 228 (1988).
J.O. Besenhard and R. Schollhorn, J. Power Sources 1, 267 (1976–77); see also J. Electrochem. Soc. 124, 968 (1977).
A.M. Chippindale, P.G. Dickens, and A.V. Powell, Prog. Solid State Chem. 21, 133 (1991); and A.M. Chippindale, P.G. Dickens, and A.V. Powell, J. Solid State Chem. 93, 526 (1991).
D.W. Murphy, P.A. Christian, F.J. DiSalvo, and J.V. Waszczak Carides, Inorg. Chem. 18, 2800 (1979); J. Electrochem. Soc. 126, 3 (1979); and J. Electrochem. Soc. 126, 497 (1979).
S.K. Deb, Proc. R. Soc. A304, 211 (1968).
M.S. Jagadeesh and V.D. Das, J. Non-Cryst. Solids 28, 327 (1978).
P.G. Dickens and D.J. Neild, Trans. Faraday Soc. 64, 13 (1968).
G. Travaglini and P. Wachter, Solid State Commun. 47, 217 (1983); and Solid State Commun. 42, 407 (1982).
M. Greenblatt, K.V. Ramanujachary, W.H. McCarroll, R. Neifeld, and J.V. Waszczak, Solid State Chem. 59, 149 (1985).
R.J. Colton, A.M. Guzman, and J.W. Rabalais, J. Appl. Phys. 49, 409 (1978).
L.E. Firment and A. Ferretti, Surf. Sci. 129, 155 (1983); see also V.E. Henrich, Report Prog. Phys. 48, 1481 (1985).
S.P. Mekandru and A.B. Anderson, J. Am. Chem. Soc. 110, 2061 (1988).
P. Pichat, M.N. Mozzanega, and C. Hoang-Van, J. Phys. Chem. 92, 467 (1988).
P.P. Edwards and C.N.R. Rao, The Metallic and Non-Metallic States of Matter (London: Taylor and Francis, 1985), p. 287.
I. Hamberg and C.G. Granqvist, J. Appl. Phys. 60, 123 (1986).
R. Erre, M.H. Legay, and J.J. Fripiat, Surf. Sci. 127, 69 (1983).
D. Tinet, P. Canesson, H. Estrade, and J.J. Fripiat, J. Phys. Chem. Solids 41, 583 (1979).
M. Rothschild and A.R. Forte, Appl. Phys. Lett. 59, 1790 (1991).
Z. Hussain, J. Mater. Res. 16, 2695 (2001).
L. Tichy, E. Sleeckx, P. Nagels, and H. Ticha, Philos. Mag. B73, 213 (1996).
E. Burstein, Phys. Rev. 93, 632 (1954).
T.S. Moss, Proc. Phys. Soc. London B 67, 775 (1954).
P.J.L. Herve and L.K.J. Vandamme, J. Appl. Phys. 77, 5476 (1995).
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); see also J. Phys. Soc. Jpn. 55, 137 (1973).
T. Skettrup, Phys. Rev. B18, 2622 (1978).
G.A. Medvedkin, Y.V. Rud, and M.A. Tairov, Phys. Status Solidi B144, 809 (1987).
T. Shioda, S. Chichibu, T. Irie, and H. Nakanishi, J. Appl. Phys. 80, 1106 (199).
M.V. Kurik, Phys. Status Solidi (a) 8, 9 (1971).
D. Emin, Phys. Rev. B48, 13691 (1993).
C. Bechinger, M.S. Burdis, and J.G. Zhang, Solid State Commun. 101, 753 (1997).
J.G. Zhang, D.K. Benson, C.E. Tracy, S.K. Deb, A.W. Czanderna, and C. Bechinger, J. Electrochem. Soc. 144, 2022 (1997).
J.B. Goodenough, Progress in Solid State Chemistry, ed. H. Reiss (London: Pergamon, 1971), vol. 5, p. 145.
O.F. Schirmer and E. Salje, Solid State Commun. 33, 333 (1980).
E. Saje and B. Guttler, Philos. Mag. B50, 607 (1984).
C.H. Grein and S. John, Phys. Rev. B36, 7457 (1987).
M. Green and Z. Hussain, J. Appl. Phys. 69, 7788 (1991).
N.F. Mott and E.A. Davis, eds., Electronic Processes in Non-Crystalline Materials, (Oxford: Oxford University Press, 1979), pp. 272–300; and Philos. Mag. 22, 903 (1970).
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).
B.W. Faughnan and R.S. Crandall, Topics in Applied Physics, ed. J.I. Pankove (Berlin: Springer-Verlag, 1980), pp. 181–211.
G.M. Ramans, J.V. Gabrusenoks, A.R. Lusis, and A.A. Patmalnieks, J. Non-Cryst. Solids 90, 637 (1987).
G.M. Ramans, J.V. Gabrusenoks, and A.A. Veispals, Phys. Status Solidi (a), 74, K41 (1982).
J.J. Kleperis, J.V. Gabrusenoks, A.R. Lusis, and G.M. Ramans, Jzv. Akad. Nauk Latv. SSR, Ser. Fiz. I Tekh. Nauk 5, 61 (1982).
A.I. Gavrilyuk, A.A. Mansurov, and F.A. Chudnovskii, Sov. Tech. Phys. Lett. 10, 292 (1984).
B.W. Faughnan, R.S. Crandall, and P.M. Heyman, RCA Rev. 36, 177 (1975).
T. Yoshimura, J. Appl. Phys. 57, 911 (1985).
E. Salje and G. Hoppmann, Philos. Mag. B43, 105 (1981); see also G. Hoppman and E. Salje, Optics Commun. 30, 199 (1979).
S. Yamada, Y. Hiruta, N. Suzuki, K. Urabe, M. Kitao, and K. Toyada, Jpn. J. Appl. Phys. 24, 142 (1985).
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Hussain, Z. Optical and electrochromic properties of annealed lithium-molybdenum-bronze thin films. J. Electron. Mater. 31, 615–630 (2002). https://doi.org/10.1007/s11664-002-0133-4
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DOI: https://doi.org/10.1007/s11664-002-0133-4