Hostname: page-component-78c5997874-j824f Total loading time: 0 Render date: 2024-11-09T07:22:39.425Z Has data issue: false hasContentIssue false
  • English
  • Français

Transition Metal Ion Species in Glass: A Comparison of Optical Absorption and Luminescence Evidence

Published online by Cambridge University Press:  25 February 2011

William B. White  and
Diane S. Knight
William B. White
Affiliation:
Materials Research Laboratory, The Pennsylvania State University, University Park, PA 16802
Diane S. Knight
Affiliation:
Materials Research Laboratory, The Pennsylvania State University, University Park, PA 16802
Get access

Abstract

Optical absorption spectra of d-d transitions can be interpreted through crystal field theory as evidence for at least four kinds of species: traditional network modifier ions (Mn2+, Fe2+, and Ni2+), octahedral complexes (Cr3+, Mn3+), tetrahedral complexes (Co2+, Fe3+), and network-forming ions (Ti4+, Fe3+). Absorption spectra measure only majority species since crystal field bands are broad and overlapping. Luminescence spectra reveal minority species if these species happen to be efficient emitters under laser excitation. Doublet-quartet emission bands (Cr3+) are independent of crystal field but allow the distinction between species because of small differences in bonding which shifts the Racah B parameter. Quartet-sextet emission (Mn2+, Fe3+) is strongly dependent on coordination number and bond lengths. Qualitative, but not quantitative, changes in speciation can be followed as glass composition is varied. Conceptually, the complexation of transition metal ions in insulator glasses results from a competition between the transition metal and the glass-forming framework for p-orbital electrons of non-bridging oxygens. Complexation is further enhanced in clustered glasses where the ions segregate into the more depolymerized units.

Type
Articles
Information
MRS Online Proceedings Library (OPL) , Volume 61: Symposium P – Defects in Glasses , 1985 , 283
Copyright
Copyright © Materials Research Society 1986

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

1. Weyl, W.A., Coloured Glasses (Society of Glass Technology, Sheffield, 1951).Google Scholar
2. Bates, T., in Modern Aspects of the Vitreous State, edited by Mackenzie, J.D. (Butterworths, London, 1962), p. 195.Google Scholar
3. Wong, J. and Angell, C.A., Glass Structure by Spectroscopy, (Marcel Dekker, New York, 1976).Google Scholar
4. Nelson, C., Furukawa, T., and White, W.B., Mat. Res. Bull. 18, 959 (1983).CrossRefGoogle Scholar
5. Cooper, A.R. Jr., J. Non-Cryst. Solids 49, 1 (1982). -CrossRefGoogle Scholar
6. Weber, M.J., in Laser Spectroscopy of Ions and Molecules in Solids, edited by Yen, W.M. and Selzer, P.M. (Springer-Verlag, Heidelberg, 1982).Google Scholar
7. Brawer, S.A. and White, W.B., Mat. Res. Bull. 12, 281 (1977).CrossRefGoogle Scholar
8. Brawer, S.A. and White, W.B., J. Mat. Sci. 13, 1907 (1978).CrossRefGoogle Scholar
9. Berretz, M. and Holt, S.L., J. Amer. Ceram. Soc. 61, 136 (1978).CrossRefGoogle Scholar
10. Paul, A., J. Mat. Sci. 10, 692 (1975).CrossRefGoogle Scholar
11. Tischer, R.E., J. Chem_.Phys. 48, 4291 (1968).CrossRefGoogle Scholar
12. Knight, D.S. and White, W.B., unpublished work.Google Scholar
13. Landry, R.J., Fournier, J.T., and Young, C.G., J. Chem. Phys. 46, 1285 (1967).CrossRefGoogle Scholar
14. Andrews, L.J., Lempicki, A., and McCollum, B.C., J. Chem. Phys. 74, 5526 (1981).CrossRefGoogle Scholar
15. Nelson, C. and White, W.B., Geochim. Cosmochim. Acta 44, 887 (1980).CrossRefGoogle Scholar
16. Paul, A., Phys. Chem. Glasses 11, 168 (1970).Google Scholar
17. Holmes, O.G. and McClure, D.S., J. Chem. Phys. 26, 1686 (1957).Google Scholar
18. Sugano, S., Tanabe, Y., and Kamimura, H., Multiplets of Transition Metal Ions in Crystals, (Academic Press, New York, 1970, p. 124.Google Scholar
19. Nelson, C. and White, W.B., submitted to J. Mat. Res.Google Scholar
20. Furukawa, T. and White, W.B., Phys. Chem. Glasses 20, 69 (1979).Google Scholar
21. Sandstrom, D.R., Lytle, F.W., Wei, P.S.P., Greegor, R.B., Wong, J., and Schultz, P., J. Non-Cryst. Solids 41, 201 (1980).CrossRefGoogle Scholar
22. Weeks, R.A., Underwood, J.R., Jr. and Giegengack, R., J. Non-Cryst. Solids 67, 593 (1984).CrossRefGoogle Scholar
23. Kurkjian, C.R. and Sigety, E.A., Phys. Chem. Glasses 9, 73 (1968).Google Scholar
24. Kinawi, A.A., J. Inorg. Nucl. Chem. 43, 1989 (1981).-CrossRefGoogle Scholar
25. Park, J.W. and Chen, H., Phys. Chem. Glasses 23, 107 (1982).Google Scholar
26. Fox, K.E., Furukawa, T., and White, W.B., Phys. Chem. Glasses 23, 169 (1982).Google Scholar
27. Fox, K.E., Furukawa, T., and White, W.B., J. Amer. Ceram. Soc. 64, C–42 (1981).Google Scholar
28. White, W.B., Matsumura, M., Linnehan, D.G., Furukawa, T., and Chandrasekhar, B.K., submitted to Amer. Mineral.Google Scholar
29. Edwards, R.J., Paul, A., and Douglas, R.W., Phys. Chem. Glasses 13, 137 (1972).Google Scholar
30. Minser, D.G., Walden, B., and White, W.B., J. Amer. Ceram. Soc. 67, C–47 (1984).CrossRefGoogle Scholar
31. Bingham, K. and Parke, S., Phys. Chem. Glasses 6, 224 (1965).Google Scholar
32. Turner, W.H. and Turner, J.E., J. Amer. Ceram. Soc. 53, 329 (1970).CrossRefGoogle Scholar
33. Paul, A. and Douglas, R.W., Phys. Chem. Glasses 8, 233 (1967).Google Scholar
34. Paul, A. and Tiwari, A.N., J. Mat. Sci. 9, 1057 (1974).CrossRefGoogle Scholar
35. Ahmed, A.A. and Abbas, A.F., J. Amer. Ceram. Soc. 66, 434 (1983).CrossRefGoogle Scholar
36. Berkes, J.S. and White, W.B., Phys. Chem. Glasses 7, 191 (1966).Google Scholar
37. Nelson, C. and White, W.B., submitted to Geochim. Cosmochim. ActaGoogle Scholar