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Optical and electrochromic properties of heated and annealed MoO3 thin films

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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.

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References

  1. Y.A. Yang, Y.W. Cao, B.H. Loo, and J.N. Yao, J. Phys. Chem. B 102, 9392 (1998).

    Article  CAS  Google Scholar 

  2. Z.S. Guan, J.N. Yao, Y.A. Yang, and B.H. Loo, J. Electroanal. Chem. 443, 175 (1998).

    Article  CAS  Google Scholar 

  3. D.A. Wruck and M. Rubin, J. Electrochem. Soc. 140, 1097 (1993).

    Article  CAS  Google Scholar 

  4. L. Yiting, D. Wen, Z. Jinwei, and S. Xinqi, Axue Huaxue (Chinese) 11, 28 (1996).

    Google Scholar 

  5. A. Abdellaoui, L. Martin, and A. Donnadieu, Phys. Status Solidi A 109, 455 (1988).

    Article  CAS  Google Scholar 

  6. J.S.E.M. Svesson and C.G. Granqvist, Proc. SPIE 502, 30 (1984).

    Article  Google Scholar 

  7. 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.

  8. A.M. Anderson, C.G. Granquvist, and J.R. Stevens, Appl. Opt. 28, 3295 (1989); SPIE 1016, 41 (1988).

    Article  Google Scholar 

  9. M.S. Whittingham, Prog. Solid State Chem. 12, 41 (1978).

    Article  CAS  Google Scholar 

  10. C. Julien, Mater. Sci. Eng. B 6, 9 (1991).

    Article  Google Scholar 

  11. 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.

  12. L. Campanella and G. Pistoia, J. Electrochem. Soc. 118, 1905 (1971).

    Article  CAS  Google Scholar 

  13. M.S. Whittingham, J. Electrochem. Soc. 122, 713 (1975).

    Article  CAS  Google Scholar 

  14. V.A. Ioffe, I.B. Patrina, and E.V. Zelenetskaya, Phys. Status Solidi 37, 425 (1970).

    Article  CAS  Google Scholar 

  15. N. Koshida, K. Ohtaka, M. Ando, M. Komuro, and N. Atoda, Jpn. J. Appl. Phys., Part I 29, 2299 (1990).

    Article  CAS  Google Scholar 

  16. M. Hashimoto, S. Watanuki, N. Koshida, M. Komuro, and N. Atoda, Jpn. J. Appl. Phys., Part I 35, 3665 (1996).

    Article  CAS  Google Scholar 

  17. N. Koshida, K. Ichinose, K. Ohtaka, M. Komuro, and N. Atoda, J. Vac. Sci. Technol. B 8, 1093 (1990).

    Article  CAS  Google Scholar 

  18. N. Koshida, K. Yoshida, S. Watanuki, M. Komuro, and N. Atoda, Jpn. J. Appl. Phys., Part I 30, 3246 (1991).

    Article  CAS  Google Scholar 

  19. N. Koshida, S. Watanuki, K. Yoshida, K. Endo, M. Komuro, and N. Atoda, Jpn. J. Appl. Phys., Part I 31, 4483 (1992).

    Article  CAS  Google Scholar 

  20. M.R. Tubbs, Phys. Status Solidi A 21, 253 (1974).

    Article  CAS  Google Scholar 

  21. F.G.K. Baucke and J.A. Duffy, Chem. Br. 21, 643 (1985).

    CAS  Google Scholar 

  22. C.G. Granqvist, Solid State Ionics 53-56, 479 (1992).

    Article  Google Scholar 

  23. 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).

    Google Scholar 

  24. G. Travaglini, P. Wachter, J. Marcus, and C. Schlenker, Solid State Commun. 37, 599 (1981); Solid State Commun. 42, 407 (1982).

    Article  CAS  Google Scholar 

  25. G. Travaglini and P. Wachter, Solid State Commun. 47, 217 (1983).

    Article  CAS  Google Scholar 

  26. M. Greenblatt, K.V. Ramanujachary, W.H. McCarroll, R. Neifeld, and J.V. Waszczak, Solid State Chem. 59, 149 (1985).

    Article  CAS  Google Scholar 

  27. W.B. Jackson, N.M. Johnson, and D.K. Biegelsen, Appl. Phys. Lett. 43, 195 (1983).

    Article  CAS  Google Scholar 

  28. V. Wittwer, O.F. Schirmer, and P. Schlotter, Solid State Com-mun. 25, 977 (1978).

    Article  CAS  Google Scholar 

  29. B.K. Chakraverty, J. Phys. 42, 1351 (1981).

    Article  CAS  Google Scholar 

  30. P.A. Gillet, J.L. Fourquet, and O. Bohnke, Mater. Res. Bull. 27, 1145 (1992).

    Article  CAS  Google Scholar 

  31. Z. Hussain, Ph.D. Thesis, University of London, London, United Kingdom (2000).

  32. H.I. Evans, Ph.D. Thesis, University of London, London, United Kingdom (1987).

  33. O. Bohnke and G. Robert, Solid State Ionics 6, 115 (1982).

    Article  CAS  Google Scholar 

  34. N. Miyata and S. Akiyashi, J. Appl. Phys. 58, 1651 (1985).

    Article  CAS  Google Scholar 

  35. M.A. Osman, A. Othman, and M.A. Abd-Alla, J. Phys. D: Appl. Phys. 24, 1203 (1991).

    Article  CAS  Google Scholar 

  36. S.K. Deb and J.A. Chopoorian, J. Appl. Phys. 37, 4818 (1966).

    Article  CAS  Google Scholar 

  37. Y. Hiruta, M. Kitao, and S. Yamada, Jpn. J. Appl. Phys. 23, 1624 (1984).

    Article  CAS  Google Scholar 

  38. K.H. Hellwege and A.M. Hellwege, Landolt-Bornstein III (Springer Verlag, Berlin, Germany, 1975), Vol. 7, pp. 488 and 496.

  39. G. Hagg and A. Magneli, Rev. Pure Appl. Chem. 4, 235 (1954).

    CAS  Google Scholar 

  40. D.L. Neirk, J.C. Fagerli, M.L. Smith, D. Mosman, and T.C. De Vore, J. Mol. Struct. 244, 165 (1991).

    Article  Google Scholar 

  41. M. Green and Z. Hussain, J. Appl. Phys. 69, 7788 (1991).

    Article  CAS  Google Scholar 

  42. 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.

  43. 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.

  44. 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.

  45. Ohba, Shun-Ichi Ikawa, and Shun-Ichi, J. Appl. Phys. 64, 4141 (1988).

    Article  CAS  Google Scholar 

  46. D.L. Wood and T. Tauc, Phys. Rev. B 5, 3144 (1972).

    Article  Google Scholar 

  47. M. Anwar and C.A. Hogarth, Phys. Status Solidi A 109, 469 (1988).

    Article  CAS  Google Scholar 

  48. S.K. Deb, Proc. R. Soc. A 304, 211 (1968).

    Google Scholar 

  49. M.S. Jagadeesh and V. Damodara Das, J. Non-Cryst. Solids 28, 327 (1978).

    Article  CAS  Google Scholar 

  50. A. Madan and M. Shaw, The Physics and Applications of Amorphous Semiconductors (Academic Press, New York, 1988).

    Google Scholar 

  51. J. Tauc, in Optical Properties of Solids, edited by F.A. Abeles (North-Holland, Amsterdam, The Netherlands, 1971).

  52. G.S. Nadkarni and J.G. Simmons, J. Appl. Phys. 43, 3741 (1972).

    Article  CAS  Google Scholar 

  53. L. Kihlborg, Ark. Kemi 21, 443 (1963).

    CAS  Google Scholar 

  54. P.G. Dickens and D.J. Neild, Trans. Faraday Soc. 64, 13 (1968).

    Article  CAS  Google Scholar 

  55. O. Bohnke, G. Frand, M. Fromm, J. Weber, and O. Greim, Appl. Surf. Sci. 93, 45 (1996)

    Article  CAS  Google Scholar 

  56. S.K. Deb, Philos. Mag. 27, 801 (1973).

    Article  CAS  Google Scholar 

  57. B.A. Anderson, Y. Kim, D.W. Ewing, R.K. Grasselli, and M. Tenhover, Surf. Sci. 134, 237 (1983).

    Article  CAS  Google Scholar 

  58. 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).

    CAS  Google Scholar 

  59. P.K. Gupta and K.L. Chopra, Appl. Phys. Lett. 51, 1527 (1987); see also J. Appl. Phys. 62, 4273 (1987).

    Article  CAS  Google Scholar 

  60. G. Hollinger, T.M. Duc, and A. Deneuville, Phys. Rev. Lett. 37, 1564 (1976).

    Article  CAS  Google Scholar 

  61. L. Su and Z. Lu, J. Phys. Chem. Solids 59, 1175 (1998).

    Article  CAS  Google Scholar 

  62. L. Su, L. Zhang, J. Fang, M. Xu, and Z. Lu, Sol. Energy Mater. Sol. Cells 58, 133 (1999).

    Article  CAS  Google Scholar 

  63. B. Gerand, G. Nowogrocki, J. Guenot, and M. Figlarz, J. Solid State Chem. 29, 429 (1979).

    Article  CAS  Google Scholar 

  64. B. Gerand, G. Nowogrocki, and M. Figlarz, J. Solid State Chem. 38, 312 (1981).

    Article  CAS  Google Scholar 

  65. O.F. Schirmer, J. Phys., Colloq. 6, 479 (1980).

    Google Scholar 

  66. E. Iguchi and K. Akashi, Jpn. J. Phys. Soc. 61, 3385 (1992).

    Article  CAS  Google Scholar 

  67. G. Anderson and A. Magneli, Acta. Chem. Scand. 4, 793 (1950); see also G. Anderson, Acta Chem. Scand. 7, 154 (1953).

    Article  Google Scholar 

  68. E.M. McCarron, III, J. Chem. Soc., Chem. Commun. 198, 336 (1986).

    Article  Google Scholar 

  69. H.Z. Braekken, Kristallografiya 78, 484 (1931).

    Google Scholar 

  70. Y. Shigesato, A. Murayama, T. Kamimori, and K. Matsuhiro, Appl. Surf. 33/34, 804 (1988).

    Article  Google Scholar 

  71. V.B. Krebs, Acta Crystallogr. B 28, 2222 (1972).

    Article  CAS  Google Scholar 

  72. O. Glemser and G. Lutz, Z. Anorg. Allg. Chem. 264, 17 (1951).

    Article  CAS  Google Scholar 

  73. O. Glemser, G. Lutz, and G. Meyer, Z. Anorg. Allg. Chem. 285, 173 (1956).

    Article  CAS  Google Scholar 

  74. C. Ritter, W. Muller-Warmuth, and R. Schollhorn, J. Chem. Phys. 83, 6130 (1985).

    Article  CAS  Google Scholar 

  75. F. Endres and G. Schwitzgebel, Electrochim. Acta 43, 431 (1998).

    Article  CAS  Google Scholar 

  76. 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).

    Google Scholar 

  77. A. Guerfi, R.W. Paynter, and Le H. Dao, J. Electrochem. Soc. 142, 3457 (1995).

    Article  CAS  Google Scholar 

  78. L. Kihlborg and A. Magneli, Acta Chem. Scand. 9, 471 (1955).

    Article  CAS  Google Scholar 

  79. Y. Shigesato, Jpn. J. Appl. Phys. 30, 145 (1991).

    Article  Google Scholar 

  80. P.F. Carcia and E.M. McCarron, III, Thin Solid Films 155, 53 (1987).

    Article  CAS  Google Scholar 

  81. M. Shiojiri, T. Miyano, and C. Kaito, Jpn. J. Appl. Phys. 18, 1937 (1979); Jpn. J. Appl. Phys. 17, 567 (1978).

    Article  CAS  Google Scholar 

  82. 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.

  83. A. Balerna, E. Bernieri, E. Burattini, A. Kuzmin, A. Lusis, J. Purans, and P. Cikmach, Nucl. Instrum. Methods Phys. Res. A 308, 234 (1991).

    Article  Google Scholar 

  84. J.V. Gabrusenoks, P.D. Chikmach, A.R. Lusis, J.J. Kleperis, and G.M. Ramans, Solid State Ionics 14, 25 (1984).

    Article  Google Scholar 

  85. F. Bonino, L. Peraldo Bicelli, B. Rivolta, M. Lazzari, and F. Festorazzi, Solid State Ionics 17, 21 (1985).

    Article  CAS  Google Scholar 

  86. J.T. Szymanski and A.C. Roberts, Can. Mineral. 22, 681 (1984).

    CAS  Google Scholar 

  87. J.R. Gunter, J. Solid State Chem. 5, 354 (1972).

    Article  Google Scholar 

  88. J.S.E.M. Svensson, D.K. Benson, and C.E. Tracy, SPIE 1016, 19 (1988).

    Google Scholar 

  89. F. Harb, B. Gerand, G. Nowogrocki, and M. Figlarz, Solid State Ionic 32/33, 84 (1989).

    Article  Google Scholar 

  90. O. Bertrand, N. Floquet, and D. Jacquot, Surf. Sci. 164, 305 (1985).

    Article  CAS  Google Scholar 

  91. P.K. Shen, J. Syed-Bokhari, and A.C.C. Tseung, J. Electrochem. Soc. 138, 2778 (1991); J. Mater. Chem. 2, 1141 (1992).

    Article  CAS  Google Scholar 

  92. C. Julien, L. El-Farh, M. Balkanski, O. Md. Hussain, and G.A. Nazri, Appl. Surf. Sci. 65/66, 325 (1993).

    Article  Google Scholar 

  93. 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).

    Article  CAS  Google Scholar 

  94. T. Hirata, Appl. Surf. Sci. 40, 179 (1989).

    Article  CAS  Google Scholar 

  95. F. Kumada, M. Okamoto, M. Baba, and T. Ikeda, Jpn. J. Appl. Phys. 25, L574 (1986).

    Article  Google Scholar 

  96. E.W. Serwicka, Crit. Rev. Surf. Chem. 1, 27 (1990).

    CAS  Google Scholar 

  97. A. Magneli, Acta Crystallogr. 6, 495 (1953).

    Article  CAS  Google Scholar 

  98. R. Juryska, Phys. Status Solidi A 72, K161 (1975).

    Article  Google Scholar 

  99. L.E. Firment and A. Ferretti, Surf. Sci. 129, 155 (1983); also see V.E. Henrich, Rep. Prog. Phys. 48, 1481 (1985).

    Article  CAS  Google Scholar 

  100. D. Tinet, P. Canesson, H. Estrade, and J.J. Fripiat, J. Phys. Chem. Solids 41. 583 (1979).

    Article  Google Scholar 

  101. P. Pichat, M-N. Mozzanega, and C. Hoang-Van, J. Phys. Chem. 92, 467 (1988).

    Article  CAS  Google Scholar 

  102. R. Erre, M.H. Legay, and J.J. Fripiat, Surf. Sci. 127, 69 (1983).

    Article  CAS  Google Scholar 

  103. J.W. Rabalais, R.J. Colton, and A.M. Guzman, Chem. Phys. Lett. 29, 131 (1974).

    Article  CAS  Google Scholar 

  104. M. Rothschild and A.R. Forte, Appl. Phys. Lett. 59, 1790 (1991).

    Article  CAS  Google Scholar 

  105. Electronic Processes in Non-Crystalline Materials, edited by N.F. Mott and E.A. Davis (Oxford University, Oxford, United Kingdom, 1979), p. 272.

  106. S.K. Deb, Sol. Energy Mater. Sol. Cells 39, 191 (1995).

    Article  CAS  Google Scholar 

  107. A. Nakamura, K. Nakada, Y. Ito, and E. Koishi, J. Appl. Phys. 57, 135 (1985).

    Article  CAS  Google Scholar 

  108. E.A. Davis and N.F. Mott, Philos. Mag. 22, 903 (1970).

    Article  CAS  Google Scholar 

  109. 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.

  110. L. Tichy, E. Sleeckx, P. Nagels, and H. Ticha, Philos. Mag. B 73, 213 (1996).

    Article  CAS  Google Scholar 

  111. 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.

  112. J.I. Pankove, Phys. Rev. 140, A2059 (1965).

    Article  CAS  Google Scholar 

  113. D. Redfield and M.A. Afromowitz, Appl. Phys. Lett. 11, 138 (1967).

    Article  CAS  Google Scholar 

  114. S. John and C.H. Grein, Rev. Solid State Sci. 4, 1 (1990).

    CAS  Google Scholar 

  115. J. Lipavicius, E. Cijauskas, and A. Audzijonis, Phys. Status Solidi A 148, K97 (1988).

    Article  Google Scholar 

  116. F.A. Shroder, Acta Crystallogr. B 31, 2294 (1975).

    Article  Google Scholar 

  117. T. Skettrup, Phys. Rev. B 18, 2622 (1978).

    Article  CAS  Google Scholar 

  118. T. He, P. Ehrhart, and P. Meuffels, J. Appl. Phys. 79, 3219 (1996).

    Article  CAS  Google Scholar 

  119. A. Sumi and Y. Toyozawa, J. Phys. Soc. Jpn. 31, 342 (1971); 55, 137 (1973).

    Article  CAS  Google Scholar 

  120. G.A. Medvedkin, Y.V. Rud, and M.A. Tairov, Phys. Status Solidi B 144, 809 (1987).

    Article  CAS  Google Scholar 

  121. T. Shioda, S. Chichibu, T. Irie, and H. Nakanishi, J. Appl. Phys. 80, 1106 (1996).

    Article  CAS  Google Scholar 

  122. M.V. Kurik, Phys. Status Solidi A 8, 9 (1971).

    Article  CAS  Google Scholar 

  123. D.I. Desnica, M. Kranjcec, and B. Celustka, J. Phys. Chem. Solids 52, 915 (1991).

    Article  CAS  Google Scholar 

  124. H. Mahr, Phys. Rev. 125, 1510 (1962).

    Article  CAS  Google Scholar 

  125. D. Emin, Phys. Rev. B 48, 13691 (1993).

    Article  CAS  Google Scholar 

  126. T.H. Fleisch and G.J. Mains, J. Chem. Phys. 76, 780 (1982).

    Article  CAS  Google Scholar 

  127. A.W. Faughnan, R.S. Crandall, and P.M. Heyman, RCA Rev. 36, 177 (1975).

    CAS  Google Scholar 

  128. J.M. Berak and M.J. Sienko, J. Solid State Chem. 2, 109 (1970).

    Article  CAS  Google Scholar 

  129. T. Masumi, Prog. Theor. Phys. Suppl. 22, 57 (1975).

    Google Scholar 

  130. E. Salje and B. Guttler, Philos. Mag. B 50, 607 (1984).

    Article  CAS  Google Scholar 

  131. H. Demiryont and S.C. Schulz, SPIE 1149, 28 (1989).

    CAS  Google Scholar 

  132. J.B. Goodenough, in Progress in Solid State Chemistry, edited by H. Reiss (Pergamon, London, United Kingdom, 1971), Vol. 5, p. 145.

  133. G.S. Nadkarni and J.G. Simmons, J. Appl. Phys. 41, 545 (1970); see also J. Appl. Phys. 43, 3741 (1972).

    Article  CAS  Google Scholar 

  134. 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).

    Article  CAS  Google Scholar 

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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

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