Abstract

Time-resolved photoluminescence (PL) on excitation with an ArF excimer laser and IR–vacuum UV optical absorption induced by irradiation of an ArF excimer laser of commercially available CaF2 single crystals fabricated by four different manufacturers were measured. Intrinsic PL that was due to self-trapped excitons generated by band-to-band excitation by two-photon absorption processes was observed in all samples. In addition, most samples showed PL originating from traces of lanthanoid (Ln) impurities, Ce3+, Eu2+ (blue emission), or Tb3+ (yellow-green emission). The PL of Ce3+ and Eu2+ had no correlation with color-center formation; however, intense absorption bands arising from an F- center associated with a trivalent yttrium ion (YFC) were necessarily induced in the samples that showed yellow-green PL of Tb3+ under irradiation by ArF excimer laser light. When the yellow-green fluorescent samples were irradiated with ArF excimer laser light, the PL intensity of Tb3+ and the induced absorption that was due to YFC increased with the irradiated pulse number, and their growth was found to conform to a first-order kinetics. It was concluded that photoelectrons were released from Tb2+ ions by ArF excimer laser irradiation, and the resulting electrons were trapped at the site of a fluorine vacancy neighboring on Y3+. Therefore the intensity of yellow-green PL of Tb3+ is proposed as an index for diagnosis of resistance to ArF excimer laser damage in CaF2 single crystals.

© 1999 Optical Society of America

Full Article  |  PDF Article

References

  • View by:
  • |
  • |
  • |

  1. W. Hayes and A. M. Stoneham, “Color centers,” in Crystals with the Fluorite Structure, W. Hayes, ed. (Oxford U. Press, London, 1974), pp. 185–280.
  2. P. Görlich, H. Karras, and R. Lehmann, “Über die Eigenschaften der Erdalkalihalogenide vom Flusspat-Type (I),” Phys. Status Solidi 1, 389–440 (1961).
    [CrossRef]
  3. R. T. Williams and E. J. Friebele, “CaF2, SrF2, BaF2,” in Vol. 3 of CRC Handbook of Laser Science and Technology, M. J. Weber, ed. (CRC Press, Boca Raton, Florida, 1986), pp. 309–310.
  4. T. Kamikawa and K. Ozawa, “Induced color centers in CaF2 crystals irradiated with neutrons at liquid nitrogen temperature,” J. Phys. Soc. Jpn. 24, 115–119 (1968).
    [CrossRef]
  5. P. Görlich, H. Karras, C. Symanowski, and P. Ullmann, “The color center absorption of x-ray colored alkaline earth fluoride crystals,” Phys. Status Solidi 25, 93–101 (1968).
    [CrossRef]
  6. J. H. Beaumont, W. Hayes, D. L. Kirk, and G. P. Summers, “An investigation of trapped holes and trapped excitons in alkaline earth fluorides,” Proc. R. Soc. London, Ser. A 315, 69–97 (1970).
    [CrossRef]
  7. C. R. A. Catlow, “Radiation damage and photochromism in the alkaline earth fluorides,” J. Phys. C 12, 969–988 (1979).
    [CrossRef]
  8. W. Hayes and R. F. Lombourn, “Production of F and F-aggregate centers in CaF2 and SrF2 by irradiation,” Phys. Status Solidi B 57, 693–699 (1973).
    [CrossRef]
  9. A. Mukaji, G. A. Tanton, and J. E. Williams, “X-ray induced F-centers in CaF2,” Phys. Status Solidi 22, K19–K23 (1967).
    [CrossRef]
  10. Y. Kazumata, “Self-trapped holes in neutron irradiated CaF2 and BaF2 crystals,” Phys. Status Solidi 26, K119–K122 (1968).
    [CrossRef]
  11. R. F. Marzke and R. L. Mieher, “Electron-nuclear double resonance of the self-trapped hole in CaF2 and BaF2,” Phys. Rev. 182, 453–458 (1969).
    [CrossRef]
  12. J. Sierro, “Paramagnetic resonance of the Vf center in CaF2,” Phys. Rev. 138, A648–A650 (1964).
    [CrossRef]
  13. W. Assmus and W. Dreybrodt, “Influence of lattice vibrations on the hyperfine structure constants of Vk- and Vf-centers in earth alkaline fluorides,” Phys. Status Solidi 34, 183–193 (1969).
    [CrossRef]
  14. W. J. Scouler and A. Smakula, “Coloration of pure and doped calcium fluoride crystals at 20 °C and 190 °C,” Phys. Rev. 120, 1154–1166 (1960).
    [CrossRef]
  15. P. Gorlich, H. Karras, W. Ludke, H. Mothes, and R. Reimann, “Coloration of yttrium-doped CaF2 and SrF2 crystals by x-ray irradiation,” Phys. Status Solidi 3, 478–484 (1963).
    [CrossRef]
  16. C. H. Anderson and E. S. Sabisky, “EPR studies of photochromic CaF2,” Phys. Rev. B 3, 527–536 (1971).
    [CrossRef]
  17. D. L. Staebler and S. E. Schnatterly, “Optical studies of a photochromic color center in rare-earth-doped CaF2,” Phys. Rev. B 3, 516–526 (1971).
    [CrossRef]
  18. R. C. Alig, “Theory of photochromic centers in CaF2,” Phys. Rev. B 3, 536–545 (1971).
    [CrossRef]
  19. N. F. Borrelli, C. Smith, D. C. Allan, and T. P. Seward III, “Densification of fused silica under 193-nm excitation,” J. Opt. Soc. Am. B 14, 1606–1615 (1997).
    [CrossRef]
  20. G. H. Dieke and H. M. Crosswhite, “The spectra of doubly and triply ionized rare earths,” Appl. Opt. 2, 675–686 (1963).
    [CrossRef]
  21. K. S. Song and R. T. Williams, “Alkaline earth fluorides,” in Self-Trapped Excitons (Springer-Verlag, Berlin, 1996) pp. 96–122.
  22. R. T. Williams, M. N. Kabler, W. Hayes, and J. P. Stott, “Time-resolved spectroscopy of self-trapped excitons in fluorite crystals,” Phys. Rev. B 14, 725–740 (1976).
    [CrossRef]
  23. K. Tanimura, T. Katoh, and N. Itoh, “Lattice relaxation of highly excited self-trapped excitons in CaF2,” Phys. Rev. B 40, 1282–1287 (1989).
    [CrossRef]
  24. A. A. Kaplyanskii, V. N. Medvedev, and P. P. Feofilov, “The spectra of trivalent cerium ions in alkaline-earth fluoride crystals,” Opt. Spectrosc. 14, 351–356 (1963).
  25. M. Schlesinger and P. W. Whippey, “Investigations of 4f-5d transitions of Ce3+ in CaF2,” Phys. Rev. 171, 361–364 (1968).
    [CrossRef]
  26. S. B. Mirov, A. Yu. Dergachev, W. A. Sibley, V. B. Sigachev, A. G. Papashvili, and T. T. Basiev, “Investigation of luminescence properties of Ce:Sc:CaF2 crystals,” Mater. Sci. Forum 239–241, 227–230 (1997).
    [CrossRef]
  27. K. Kawano and R. Nakata, “X-ray excitation luminescence of the Eu ion doped into fluorite type CaF2-SrF2 and SrF2-BaF2 mixed crystal systems,” Mater. Sci. Forum 239–241, 761–764 (1997).
    [CrossRef]
  28. R. L. Amster, “Photosensitization of terbium fluorescence by europium in CaF2,” J. Electrochem. Soc. 117, 791–794 (1970).
    [CrossRef]
  29. N. Rabbiner, “Fluorescence of Tb3+,” J. Opt. Soc. Am. 55, 436–438 (1965).
    [CrossRef]
  30. L. D. Livanova, I. G. Saitkulov, and A. L. Stolov, “Summation processes for quanta in CaF2 and SrF2 single crystals activated with Tb3+ and Yb3+ ions,” Sov. Phys. Solid State 11, 750–754 (1969).
  31. M. Mizuguchi, H. Hosono, H. Kawazoe, and T. Ogawa, “Generation of optical absorption bands in CaF2 single crystals by ArF excimer laser irradiation: effect of yttrium impurity,” J. Vac. Sci. Technol. A 16, 3052–3057 (1998).
    [CrossRef]
  32. A. Smakula, “Über Erregung und Entfärburg lichtelektrisch leitender Alkalihalogenide,” Z. Phys. 59, 603–614 (1930).
    [CrossRef]
  33. H. W. Hartog and G. J. Flim, “Oscillator strength of the α- and β-band in CaF2,” Phys. Status Solidi B 50, K53–K57 (1972).
    [CrossRef]
  34. D. S. McClure and Z. Kiss, “Survey of the spectra of the divalent rare-earth ions in cubic crystals,” J. Chem. Phys. 39, 3251–3257 (1963).
    [CrossRef]
  35. J. T. Mouchovski, V. Tz. Penev, and R. B. Kuneva, “Control of the growth optimum in producing high quality CaF2 crystals by an improved Bridgman–Stockbarger technique,” Cryst. Res. Technol. 31, 727–737 (1996).
    [CrossRef]
  36. J. T. Mouchovski, I. V. Haltakov, and V. L. Lyutskanov, “Growth of ultra-violet grade CaF2 crystals and their application for excimer laser optics,” J. Cryst. Growth 162, 79 (1996).
    [CrossRef]
  37. T. Moeller, “The Lanthanides,” in Comprehensive Inorganic Chemistry, J. C. Bailar, H. J. Emeleus, R. Nyholm, and A. F. Trotman-Dickenson, eds. (Pergamon Press, Oxford, 1973), Vol. 4, pp. 1–101.

1998 (1)

M. Mizuguchi, H. Hosono, H. Kawazoe, and T. Ogawa, “Generation of optical absorption bands in CaF2 single crystals by ArF excimer laser irradiation: effect of yttrium impurity,” J. Vac. Sci. Technol. A 16, 3052–3057 (1998).
[CrossRef]

1997 (3)

S. B. Mirov, A. Yu. Dergachev, W. A. Sibley, V. B. Sigachev, A. G. Papashvili, and T. T. Basiev, “Investigation of luminescence properties of Ce:Sc:CaF2 crystals,” Mater. Sci. Forum 239–241, 227–230 (1997).
[CrossRef]

K. Kawano and R. Nakata, “X-ray excitation luminescence of the Eu ion doped into fluorite type CaF2-SrF2 and SrF2-BaF2 mixed crystal systems,” Mater. Sci. Forum 239–241, 761–764 (1997).
[CrossRef]

N. F. Borrelli, C. Smith, D. C. Allan, and T. P. Seward III, “Densification of fused silica under 193-nm excitation,” J. Opt. Soc. Am. B 14, 1606–1615 (1997).
[CrossRef]

1996 (2)

J. T. Mouchovski, V. Tz. Penev, and R. B. Kuneva, “Control of the growth optimum in producing high quality CaF2 crystals by an improved Bridgman–Stockbarger technique,” Cryst. Res. Technol. 31, 727–737 (1996).
[CrossRef]

J. T. Mouchovski, I. V. Haltakov, and V. L. Lyutskanov, “Growth of ultra-violet grade CaF2 crystals and their application for excimer laser optics,” J. Cryst. Growth 162, 79 (1996).
[CrossRef]

1989 (1)

K. Tanimura, T. Katoh, and N. Itoh, “Lattice relaxation of highly excited self-trapped excitons in CaF2,” Phys. Rev. B 40, 1282–1287 (1989).
[CrossRef]

1979 (1)

C. R. A. Catlow, “Radiation damage and photochromism in the alkaline earth fluorides,” J. Phys. C 12, 969–988 (1979).
[CrossRef]

1976 (1)

R. T. Williams, M. N. Kabler, W. Hayes, and J. P. Stott, “Time-resolved spectroscopy of self-trapped excitons in fluorite crystals,” Phys. Rev. B 14, 725–740 (1976).
[CrossRef]

1973 (1)

W. Hayes and R. F. Lombourn, “Production of F and F-aggregate centers in CaF2 and SrF2 by irradiation,” Phys. Status Solidi B 57, 693–699 (1973).
[CrossRef]

1972 (1)

H. W. Hartog and G. J. Flim, “Oscillator strength of the α- and β-band in CaF2,” Phys. Status Solidi B 50, K53–K57 (1972).
[CrossRef]

1971 (3)

C. H. Anderson and E. S. Sabisky, “EPR studies of photochromic CaF2,” Phys. Rev. B 3, 527–536 (1971).
[CrossRef]

D. L. Staebler and S. E. Schnatterly, “Optical studies of a photochromic color center in rare-earth-doped CaF2,” Phys. Rev. B 3, 516–526 (1971).
[CrossRef]

R. C. Alig, “Theory of photochromic centers in CaF2,” Phys. Rev. B 3, 536–545 (1971).
[CrossRef]

1970 (2)

J. H. Beaumont, W. Hayes, D. L. Kirk, and G. P. Summers, “An investigation of trapped holes and trapped excitons in alkaline earth fluorides,” Proc. R. Soc. London, Ser. A 315, 69–97 (1970).
[CrossRef]

R. L. Amster, “Photosensitization of terbium fluorescence by europium in CaF2,” J. Electrochem. Soc. 117, 791–794 (1970).
[CrossRef]

1969 (3)

L. D. Livanova, I. G. Saitkulov, and A. L. Stolov, “Summation processes for quanta in CaF2 and SrF2 single crystals activated with Tb3+ and Yb3+ ions,” Sov. Phys. Solid State 11, 750–754 (1969).

R. F. Marzke and R. L. Mieher, “Electron-nuclear double resonance of the self-trapped hole in CaF2 and BaF2,” Phys. Rev. 182, 453–458 (1969).
[CrossRef]

W. Assmus and W. Dreybrodt, “Influence of lattice vibrations on the hyperfine structure constants of Vk- and Vf-centers in earth alkaline fluorides,” Phys. Status Solidi 34, 183–193 (1969).
[CrossRef]

1968 (4)

Y. Kazumata, “Self-trapped holes in neutron irradiated CaF2 and BaF2 crystals,” Phys. Status Solidi 26, K119–K122 (1968).
[CrossRef]

T. Kamikawa and K. Ozawa, “Induced color centers in CaF2 crystals irradiated with neutrons at liquid nitrogen temperature,” J. Phys. Soc. Jpn. 24, 115–119 (1968).
[CrossRef]

P. Görlich, H. Karras, C. Symanowski, and P. Ullmann, “The color center absorption of x-ray colored alkaline earth fluoride crystals,” Phys. Status Solidi 25, 93–101 (1968).
[CrossRef]

M. Schlesinger and P. W. Whippey, “Investigations of 4f-5d transitions of Ce3+ in CaF2,” Phys. Rev. 171, 361–364 (1968).
[CrossRef]

1967 (1)

A. Mukaji, G. A. Tanton, and J. E. Williams, “X-ray induced F-centers in CaF2,” Phys. Status Solidi 22, K19–K23 (1967).
[CrossRef]

1965 (1)

1964 (1)

J. Sierro, “Paramagnetic resonance of the Vf center in CaF2,” Phys. Rev. 138, A648–A650 (1964).
[CrossRef]

1963 (4)

P. Gorlich, H. Karras, W. Ludke, H. Mothes, and R. Reimann, “Coloration of yttrium-doped CaF2 and SrF2 crystals by x-ray irradiation,” Phys. Status Solidi 3, 478–484 (1963).
[CrossRef]

G. H. Dieke and H. M. Crosswhite, “The spectra of doubly and triply ionized rare earths,” Appl. Opt. 2, 675–686 (1963).
[CrossRef]

A. A. Kaplyanskii, V. N. Medvedev, and P. P. Feofilov, “The spectra of trivalent cerium ions in alkaline-earth fluoride crystals,” Opt. Spectrosc. 14, 351–356 (1963).

D. S. McClure and Z. Kiss, “Survey of the spectra of the divalent rare-earth ions in cubic crystals,” J. Chem. Phys. 39, 3251–3257 (1963).
[CrossRef]

1961 (1)

P. Görlich, H. Karras, and R. Lehmann, “Über die Eigenschaften der Erdalkalihalogenide vom Flusspat-Type (I),” Phys. Status Solidi 1, 389–440 (1961).
[CrossRef]

1960 (1)

W. J. Scouler and A. Smakula, “Coloration of pure and doped calcium fluoride crystals at 20 °C and 190 °C,” Phys. Rev. 120, 1154–1166 (1960).
[CrossRef]

1930 (1)

A. Smakula, “Über Erregung und Entfärburg lichtelektrisch leitender Alkalihalogenide,” Z. Phys. 59, 603–614 (1930).
[CrossRef]

Alig, R. C.

R. C. Alig, “Theory of photochromic centers in CaF2,” Phys. Rev. B 3, 536–545 (1971).
[CrossRef]

Allan, D. C.

Amster, R. L.

R. L. Amster, “Photosensitization of terbium fluorescence by europium in CaF2,” J. Electrochem. Soc. 117, 791–794 (1970).
[CrossRef]

Anderson, C. H.

C. H. Anderson and E. S. Sabisky, “EPR studies of photochromic CaF2,” Phys. Rev. B 3, 527–536 (1971).
[CrossRef]

Assmus, W.

W. Assmus and W. Dreybrodt, “Influence of lattice vibrations on the hyperfine structure constants of Vk- and Vf-centers in earth alkaline fluorides,” Phys. Status Solidi 34, 183–193 (1969).
[CrossRef]

Basiev, T. T.

S. B. Mirov, A. Yu. Dergachev, W. A. Sibley, V. B. Sigachev, A. G. Papashvili, and T. T. Basiev, “Investigation of luminescence properties of Ce:Sc:CaF2 crystals,” Mater. Sci. Forum 239–241, 227–230 (1997).
[CrossRef]

Beaumont, J. H.

J. H. Beaumont, W. Hayes, D. L. Kirk, and G. P. Summers, “An investigation of trapped holes and trapped excitons in alkaline earth fluorides,” Proc. R. Soc. London, Ser. A 315, 69–97 (1970).
[CrossRef]

Borrelli, N. F.

Catlow, C. R. A.

C. R. A. Catlow, “Radiation damage and photochromism in the alkaline earth fluorides,” J. Phys. C 12, 969–988 (1979).
[CrossRef]

Crosswhite, H. M.

Dergachev, A. Yu.

S. B. Mirov, A. Yu. Dergachev, W. A. Sibley, V. B. Sigachev, A. G. Papashvili, and T. T. Basiev, “Investigation of luminescence properties of Ce:Sc:CaF2 crystals,” Mater. Sci. Forum 239–241, 227–230 (1997).
[CrossRef]

Dieke, G. H.

Dreybrodt, W.

W. Assmus and W. Dreybrodt, “Influence of lattice vibrations on the hyperfine structure constants of Vk- and Vf-centers in earth alkaline fluorides,” Phys. Status Solidi 34, 183–193 (1969).
[CrossRef]

Feofilov, P. P.

A. A. Kaplyanskii, V. N. Medvedev, and P. P. Feofilov, “The spectra of trivalent cerium ions in alkaline-earth fluoride crystals,” Opt. Spectrosc. 14, 351–356 (1963).

Flim, G. J.

H. W. Hartog and G. J. Flim, “Oscillator strength of the α- and β-band in CaF2,” Phys. Status Solidi B 50, K53–K57 (1972).
[CrossRef]

Gorlich, P.

P. Gorlich, H. Karras, W. Ludke, H. Mothes, and R. Reimann, “Coloration of yttrium-doped CaF2 and SrF2 crystals by x-ray irradiation,” Phys. Status Solidi 3, 478–484 (1963).
[CrossRef]

Görlich, P.

P. Görlich, H. Karras, C. Symanowski, and P. Ullmann, “The color center absorption of x-ray colored alkaline earth fluoride crystals,” Phys. Status Solidi 25, 93–101 (1968).
[CrossRef]

P. Görlich, H. Karras, and R. Lehmann, “Über die Eigenschaften der Erdalkalihalogenide vom Flusspat-Type (I),” Phys. Status Solidi 1, 389–440 (1961).
[CrossRef]

Haltakov, I. V.

J. T. Mouchovski, I. V. Haltakov, and V. L. Lyutskanov, “Growth of ultra-violet grade CaF2 crystals and their application for excimer laser optics,” J. Cryst. Growth 162, 79 (1996).
[CrossRef]

Hartog, H. W.

H. W. Hartog and G. J. Flim, “Oscillator strength of the α- and β-band in CaF2,” Phys. Status Solidi B 50, K53–K57 (1972).
[CrossRef]

Hayes, W.

R. T. Williams, M. N. Kabler, W. Hayes, and J. P. Stott, “Time-resolved spectroscopy of self-trapped excitons in fluorite crystals,” Phys. Rev. B 14, 725–740 (1976).
[CrossRef]

W. Hayes and R. F. Lombourn, “Production of F and F-aggregate centers in CaF2 and SrF2 by irradiation,” Phys. Status Solidi B 57, 693–699 (1973).
[CrossRef]

J. H. Beaumont, W. Hayes, D. L. Kirk, and G. P. Summers, “An investigation of trapped holes and trapped excitons in alkaline earth fluorides,” Proc. R. Soc. London, Ser. A 315, 69–97 (1970).
[CrossRef]

Hosono, H.

M. Mizuguchi, H. Hosono, H. Kawazoe, and T. Ogawa, “Generation of optical absorption bands in CaF2 single crystals by ArF excimer laser irradiation: effect of yttrium impurity,” J. Vac. Sci. Technol. A 16, 3052–3057 (1998).
[CrossRef]

Itoh, N.

K. Tanimura, T. Katoh, and N. Itoh, “Lattice relaxation of highly excited self-trapped excitons in CaF2,” Phys. Rev. B 40, 1282–1287 (1989).
[CrossRef]

Kabler, M. N.

R. T. Williams, M. N. Kabler, W. Hayes, and J. P. Stott, “Time-resolved spectroscopy of self-trapped excitons in fluorite crystals,” Phys. Rev. B 14, 725–740 (1976).
[CrossRef]

Kamikawa, T.

T. Kamikawa and K. Ozawa, “Induced color centers in CaF2 crystals irradiated with neutrons at liquid nitrogen temperature,” J. Phys. Soc. Jpn. 24, 115–119 (1968).
[CrossRef]

Kaplyanskii, A. A.

A. A. Kaplyanskii, V. N. Medvedev, and P. P. Feofilov, “The spectra of trivalent cerium ions in alkaline-earth fluoride crystals,” Opt. Spectrosc. 14, 351–356 (1963).

Karras, H.

P. Görlich, H. Karras, C. Symanowski, and P. Ullmann, “The color center absorption of x-ray colored alkaline earth fluoride crystals,” Phys. Status Solidi 25, 93–101 (1968).
[CrossRef]

P. Gorlich, H. Karras, W. Ludke, H. Mothes, and R. Reimann, “Coloration of yttrium-doped CaF2 and SrF2 crystals by x-ray irradiation,” Phys. Status Solidi 3, 478–484 (1963).
[CrossRef]

P. Görlich, H. Karras, and R. Lehmann, “Über die Eigenschaften der Erdalkalihalogenide vom Flusspat-Type (I),” Phys. Status Solidi 1, 389–440 (1961).
[CrossRef]

Katoh, T.

K. Tanimura, T. Katoh, and N. Itoh, “Lattice relaxation of highly excited self-trapped excitons in CaF2,” Phys. Rev. B 40, 1282–1287 (1989).
[CrossRef]

Kawano, K.

K. Kawano and R. Nakata, “X-ray excitation luminescence of the Eu ion doped into fluorite type CaF2-SrF2 and SrF2-BaF2 mixed crystal systems,” Mater. Sci. Forum 239–241, 761–764 (1997).
[CrossRef]

Kawazoe, H.

M. Mizuguchi, H. Hosono, H. Kawazoe, and T. Ogawa, “Generation of optical absorption bands in CaF2 single crystals by ArF excimer laser irradiation: effect of yttrium impurity,” J. Vac. Sci. Technol. A 16, 3052–3057 (1998).
[CrossRef]

Kazumata, Y.

Y. Kazumata, “Self-trapped holes in neutron irradiated CaF2 and BaF2 crystals,” Phys. Status Solidi 26, K119–K122 (1968).
[CrossRef]

Kirk, D. L.

J. H. Beaumont, W. Hayes, D. L. Kirk, and G. P. Summers, “An investigation of trapped holes and trapped excitons in alkaline earth fluorides,” Proc. R. Soc. London, Ser. A 315, 69–97 (1970).
[CrossRef]

Kiss, Z.

D. S. McClure and Z. Kiss, “Survey of the spectra of the divalent rare-earth ions in cubic crystals,” J. Chem. Phys. 39, 3251–3257 (1963).
[CrossRef]

Kuneva, R. B.

J. T. Mouchovski, V. Tz. Penev, and R. B. Kuneva, “Control of the growth optimum in producing high quality CaF2 crystals by an improved Bridgman–Stockbarger technique,” Cryst. Res. Technol. 31, 727–737 (1996).
[CrossRef]

Lehmann, R.

P. Görlich, H. Karras, and R. Lehmann, “Über die Eigenschaften der Erdalkalihalogenide vom Flusspat-Type (I),” Phys. Status Solidi 1, 389–440 (1961).
[CrossRef]

Livanova, L. D.

L. D. Livanova, I. G. Saitkulov, and A. L. Stolov, “Summation processes for quanta in CaF2 and SrF2 single crystals activated with Tb3+ and Yb3+ ions,” Sov. Phys. Solid State 11, 750–754 (1969).

Lombourn, R. F.

W. Hayes and R. F. Lombourn, “Production of F and F-aggregate centers in CaF2 and SrF2 by irradiation,” Phys. Status Solidi B 57, 693–699 (1973).
[CrossRef]

Ludke, W.

P. Gorlich, H. Karras, W. Ludke, H. Mothes, and R. Reimann, “Coloration of yttrium-doped CaF2 and SrF2 crystals by x-ray irradiation,” Phys. Status Solidi 3, 478–484 (1963).
[CrossRef]

Lyutskanov, V. L.

J. T. Mouchovski, I. V. Haltakov, and V. L. Lyutskanov, “Growth of ultra-violet grade CaF2 crystals and their application for excimer laser optics,” J. Cryst. Growth 162, 79 (1996).
[CrossRef]

Marzke, R. F.

R. F. Marzke and R. L. Mieher, “Electron-nuclear double resonance of the self-trapped hole in CaF2 and BaF2,” Phys. Rev. 182, 453–458 (1969).
[CrossRef]

McClure, D. S.

D. S. McClure and Z. Kiss, “Survey of the spectra of the divalent rare-earth ions in cubic crystals,” J. Chem. Phys. 39, 3251–3257 (1963).
[CrossRef]

Medvedev, V. N.

A. A. Kaplyanskii, V. N. Medvedev, and P. P. Feofilov, “The spectra of trivalent cerium ions in alkaline-earth fluoride crystals,” Opt. Spectrosc. 14, 351–356 (1963).

Mieher, R. L.

R. F. Marzke and R. L. Mieher, “Electron-nuclear double resonance of the self-trapped hole in CaF2 and BaF2,” Phys. Rev. 182, 453–458 (1969).
[CrossRef]

Mirov, S. B.

S. B. Mirov, A. Yu. Dergachev, W. A. Sibley, V. B. Sigachev, A. G. Papashvili, and T. T. Basiev, “Investigation of luminescence properties of Ce:Sc:CaF2 crystals,” Mater. Sci. Forum 239–241, 227–230 (1997).
[CrossRef]

Mizuguchi, M.

M. Mizuguchi, H. Hosono, H. Kawazoe, and T. Ogawa, “Generation of optical absorption bands in CaF2 single crystals by ArF excimer laser irradiation: effect of yttrium impurity,” J. Vac. Sci. Technol. A 16, 3052–3057 (1998).
[CrossRef]

Mothes, H.

P. Gorlich, H. Karras, W. Ludke, H. Mothes, and R. Reimann, “Coloration of yttrium-doped CaF2 and SrF2 crystals by x-ray irradiation,” Phys. Status Solidi 3, 478–484 (1963).
[CrossRef]

Mouchovski, J. T.

J. T. Mouchovski, I. V. Haltakov, and V. L. Lyutskanov, “Growth of ultra-violet grade CaF2 crystals and their application for excimer laser optics,” J. Cryst. Growth 162, 79 (1996).
[CrossRef]

J. T. Mouchovski, V. Tz. Penev, and R. B. Kuneva, “Control of the growth optimum in producing high quality CaF2 crystals by an improved Bridgman–Stockbarger technique,” Cryst. Res. Technol. 31, 727–737 (1996).
[CrossRef]

Mukaji, A.

A. Mukaji, G. A. Tanton, and J. E. Williams, “X-ray induced F-centers in CaF2,” Phys. Status Solidi 22, K19–K23 (1967).
[CrossRef]

Nakata, R.

K. Kawano and R. Nakata, “X-ray excitation luminescence of the Eu ion doped into fluorite type CaF2-SrF2 and SrF2-BaF2 mixed crystal systems,” Mater. Sci. Forum 239–241, 761–764 (1997).
[CrossRef]

Ogawa, T.

M. Mizuguchi, H. Hosono, H. Kawazoe, and T. Ogawa, “Generation of optical absorption bands in CaF2 single crystals by ArF excimer laser irradiation: effect of yttrium impurity,” J. Vac. Sci. Technol. A 16, 3052–3057 (1998).
[CrossRef]

Ozawa, K.

T. Kamikawa and K. Ozawa, “Induced color centers in CaF2 crystals irradiated with neutrons at liquid nitrogen temperature,” J. Phys. Soc. Jpn. 24, 115–119 (1968).
[CrossRef]

Papashvili, A. G.

S. B. Mirov, A. Yu. Dergachev, W. A. Sibley, V. B. Sigachev, A. G. Papashvili, and T. T. Basiev, “Investigation of luminescence properties of Ce:Sc:CaF2 crystals,” Mater. Sci. Forum 239–241, 227–230 (1997).
[CrossRef]

Penev, V. Tz.

J. T. Mouchovski, V. Tz. Penev, and R. B. Kuneva, “Control of the growth optimum in producing high quality CaF2 crystals by an improved Bridgman–Stockbarger technique,” Cryst. Res. Technol. 31, 727–737 (1996).
[CrossRef]

Rabbiner, N.

Reimann, R.

P. Gorlich, H. Karras, W. Ludke, H. Mothes, and R. Reimann, “Coloration of yttrium-doped CaF2 and SrF2 crystals by x-ray irradiation,” Phys. Status Solidi 3, 478–484 (1963).
[CrossRef]

Sabisky, E. S.

C. H. Anderson and E. S. Sabisky, “EPR studies of photochromic CaF2,” Phys. Rev. B 3, 527–536 (1971).
[CrossRef]

Saitkulov, I. G.

L. D. Livanova, I. G. Saitkulov, and A. L. Stolov, “Summation processes for quanta in CaF2 and SrF2 single crystals activated with Tb3+ and Yb3+ ions,” Sov. Phys. Solid State 11, 750–754 (1969).

Schlesinger, M.

M. Schlesinger and P. W. Whippey, “Investigations of 4f-5d transitions of Ce3+ in CaF2,” Phys. Rev. 171, 361–364 (1968).
[CrossRef]

Schnatterly, S. E.

D. L. Staebler and S. E. Schnatterly, “Optical studies of a photochromic color center in rare-earth-doped CaF2,” Phys. Rev. B 3, 516–526 (1971).
[CrossRef]

Scouler, W. J.

W. J. Scouler and A. Smakula, “Coloration of pure and doped calcium fluoride crystals at 20 °C and 190 °C,” Phys. Rev. 120, 1154–1166 (1960).
[CrossRef]

Seward III, T. P.

Sibley, W. A.

S. B. Mirov, A. Yu. Dergachev, W. A. Sibley, V. B. Sigachev, A. G. Papashvili, and T. T. Basiev, “Investigation of luminescence properties of Ce:Sc:CaF2 crystals,” Mater. Sci. Forum 239–241, 227–230 (1997).
[CrossRef]

Sierro, J.

J. Sierro, “Paramagnetic resonance of the Vf center in CaF2,” Phys. Rev. 138, A648–A650 (1964).
[CrossRef]

Sigachev, V. B.

S. B. Mirov, A. Yu. Dergachev, W. A. Sibley, V. B. Sigachev, A. G. Papashvili, and T. T. Basiev, “Investigation of luminescence properties of Ce:Sc:CaF2 crystals,” Mater. Sci. Forum 239–241, 227–230 (1997).
[CrossRef]

Smakula, A.

W. J. Scouler and A. Smakula, “Coloration of pure and doped calcium fluoride crystals at 20 °C and 190 °C,” Phys. Rev. 120, 1154–1166 (1960).
[CrossRef]

A. Smakula, “Über Erregung und Entfärburg lichtelektrisch leitender Alkalihalogenide,” Z. Phys. 59, 603–614 (1930).
[CrossRef]

Smith, C.

Staebler, D. L.

D. L. Staebler and S. E. Schnatterly, “Optical studies of a photochromic color center in rare-earth-doped CaF2,” Phys. Rev. B 3, 516–526 (1971).
[CrossRef]

Stolov, A. L.

L. D. Livanova, I. G. Saitkulov, and A. L. Stolov, “Summation processes for quanta in CaF2 and SrF2 single crystals activated with Tb3+ and Yb3+ ions,” Sov. Phys. Solid State 11, 750–754 (1969).

Stott, J. P.

R. T. Williams, M. N. Kabler, W. Hayes, and J. P. Stott, “Time-resolved spectroscopy of self-trapped excitons in fluorite crystals,” Phys. Rev. B 14, 725–740 (1976).
[CrossRef]

Summers, G. P.

J. H. Beaumont, W. Hayes, D. L. Kirk, and G. P. Summers, “An investigation of trapped holes and trapped excitons in alkaline earth fluorides,” Proc. R. Soc. London, Ser. A 315, 69–97 (1970).
[CrossRef]

Symanowski, C.

P. Görlich, H. Karras, C. Symanowski, and P. Ullmann, “The color center absorption of x-ray colored alkaline earth fluoride crystals,” Phys. Status Solidi 25, 93–101 (1968).
[CrossRef]

Tanimura, K.

K. Tanimura, T. Katoh, and N. Itoh, “Lattice relaxation of highly excited self-trapped excitons in CaF2,” Phys. Rev. B 40, 1282–1287 (1989).
[CrossRef]

Tanton, G. A.

A. Mukaji, G. A. Tanton, and J. E. Williams, “X-ray induced F-centers in CaF2,” Phys. Status Solidi 22, K19–K23 (1967).
[CrossRef]

Ullmann, P.

P. Görlich, H. Karras, C. Symanowski, and P. Ullmann, “The color center absorption of x-ray colored alkaline earth fluoride crystals,” Phys. Status Solidi 25, 93–101 (1968).
[CrossRef]

Whippey, P. W.

M. Schlesinger and P. W. Whippey, “Investigations of 4f-5d transitions of Ce3+ in CaF2,” Phys. Rev. 171, 361–364 (1968).
[CrossRef]

Williams, J. E.

A. Mukaji, G. A. Tanton, and J. E. Williams, “X-ray induced F-centers in CaF2,” Phys. Status Solidi 22, K19–K23 (1967).
[CrossRef]

Williams, R. T.

R. T. Williams, M. N. Kabler, W. Hayes, and J. P. Stott, “Time-resolved spectroscopy of self-trapped excitons in fluorite crystals,” Phys. Rev. B 14, 725–740 (1976).
[CrossRef]

Appl. Opt. (1)

Cryst. Res. Technol. (1)

J. T. Mouchovski, V. Tz. Penev, and R. B. Kuneva, “Control of the growth optimum in producing high quality CaF2 crystals by an improved Bridgman–Stockbarger technique,” Cryst. Res. Technol. 31, 727–737 (1996).
[CrossRef]

J. Chem. Phys. (1)

D. S. McClure and Z. Kiss, “Survey of the spectra of the divalent rare-earth ions in cubic crystals,” J. Chem. Phys. 39, 3251–3257 (1963).
[CrossRef]

J. Cryst. Growth (1)

J. T. Mouchovski, I. V. Haltakov, and V. L. Lyutskanov, “Growth of ultra-violet grade CaF2 crystals and their application for excimer laser optics,” J. Cryst. Growth 162, 79 (1996).
[CrossRef]

J. Electrochem. Soc. (1)

R. L. Amster, “Photosensitization of terbium fluorescence by europium in CaF2,” J. Electrochem. Soc. 117, 791–794 (1970).
[CrossRef]

J. Opt. Soc. Am. (1)

J. Opt. Soc. Am. B (1)

J. Phys. C (1)

C. R. A. Catlow, “Radiation damage and photochromism in the alkaline earth fluorides,” J. Phys. C 12, 969–988 (1979).
[CrossRef]

J. Phys. Soc. Jpn. (1)

T. Kamikawa and K. Ozawa, “Induced color centers in CaF2 crystals irradiated with neutrons at liquid nitrogen temperature,” J. Phys. Soc. Jpn. 24, 115–119 (1968).
[CrossRef]

J. Vac. Sci. Technol. A (1)

M. Mizuguchi, H. Hosono, H. Kawazoe, and T. Ogawa, “Generation of optical absorption bands in CaF2 single crystals by ArF excimer laser irradiation: effect of yttrium impurity,” J. Vac. Sci. Technol. A 16, 3052–3057 (1998).
[CrossRef]

Mater. Sci. Forum (2)

S. B. Mirov, A. Yu. Dergachev, W. A. Sibley, V. B. Sigachev, A. G. Papashvili, and T. T. Basiev, “Investigation of luminescence properties of Ce:Sc:CaF2 crystals,” Mater. Sci. Forum 239–241, 227–230 (1997).
[CrossRef]

K. Kawano and R. Nakata, “X-ray excitation luminescence of the Eu ion doped into fluorite type CaF2-SrF2 and SrF2-BaF2 mixed crystal systems,” Mater. Sci. Forum 239–241, 761–764 (1997).
[CrossRef]

Opt. Spectrosc. (1)

A. A. Kaplyanskii, V. N. Medvedev, and P. P. Feofilov, “The spectra of trivalent cerium ions in alkaline-earth fluoride crystals,” Opt. Spectrosc. 14, 351–356 (1963).

Phys. Rev. (4)

M. Schlesinger and P. W. Whippey, “Investigations of 4f-5d transitions of Ce3+ in CaF2,” Phys. Rev. 171, 361–364 (1968).
[CrossRef]

R. F. Marzke and R. L. Mieher, “Electron-nuclear double resonance of the self-trapped hole in CaF2 and BaF2,” Phys. Rev. 182, 453–458 (1969).
[CrossRef]

J. Sierro, “Paramagnetic resonance of the Vf center in CaF2,” Phys. Rev. 138, A648–A650 (1964).
[CrossRef]

W. J. Scouler and A. Smakula, “Coloration of pure and doped calcium fluoride crystals at 20 °C and 190 °C,” Phys. Rev. 120, 1154–1166 (1960).
[CrossRef]

Phys. Rev. B (5)

C. H. Anderson and E. S. Sabisky, “EPR studies of photochromic CaF2,” Phys. Rev. B 3, 527–536 (1971).
[CrossRef]

D. L. Staebler and S. E. Schnatterly, “Optical studies of a photochromic color center in rare-earth-doped CaF2,” Phys. Rev. B 3, 516–526 (1971).
[CrossRef]

R. C. Alig, “Theory of photochromic centers in CaF2,” Phys. Rev. B 3, 536–545 (1971).
[CrossRef]

R. T. Williams, M. N. Kabler, W. Hayes, and J. P. Stott, “Time-resolved spectroscopy of self-trapped excitons in fluorite crystals,” Phys. Rev. B 14, 725–740 (1976).
[CrossRef]

K. Tanimura, T. Katoh, and N. Itoh, “Lattice relaxation of highly excited self-trapped excitons in CaF2,” Phys. Rev. B 40, 1282–1287 (1989).
[CrossRef]

Phys. Status Solidi (6)

P. Gorlich, H. Karras, W. Ludke, H. Mothes, and R. Reimann, “Coloration of yttrium-doped CaF2 and SrF2 crystals by x-ray irradiation,” Phys. Status Solidi 3, 478–484 (1963).
[CrossRef]

W. Assmus and W. Dreybrodt, “Influence of lattice vibrations on the hyperfine structure constants of Vk- and Vf-centers in earth alkaline fluorides,” Phys. Status Solidi 34, 183–193 (1969).
[CrossRef]

P. Görlich, H. Karras, C. Symanowski, and P. Ullmann, “The color center absorption of x-ray colored alkaline earth fluoride crystals,” Phys. Status Solidi 25, 93–101 (1968).
[CrossRef]

P. Görlich, H. Karras, and R. Lehmann, “Über die Eigenschaften der Erdalkalihalogenide vom Flusspat-Type (I),” Phys. Status Solidi 1, 389–440 (1961).
[CrossRef]

A. Mukaji, G. A. Tanton, and J. E. Williams, “X-ray induced F-centers in CaF2,” Phys. Status Solidi 22, K19–K23 (1967).
[CrossRef]

Y. Kazumata, “Self-trapped holes in neutron irradiated CaF2 and BaF2 crystals,” Phys. Status Solidi 26, K119–K122 (1968).
[CrossRef]

Phys. Status Solidi B (2)

W. Hayes and R. F. Lombourn, “Production of F and F-aggregate centers in CaF2 and SrF2 by irradiation,” Phys. Status Solidi B 57, 693–699 (1973).
[CrossRef]

H. W. Hartog and G. J. Flim, “Oscillator strength of the α- and β-band in CaF2,” Phys. Status Solidi B 50, K53–K57 (1972).
[CrossRef]

Proc. R. Soc. London, Ser. A (1)

J. H. Beaumont, W. Hayes, D. L. Kirk, and G. P. Summers, “An investigation of trapped holes and trapped excitons in alkaline earth fluorides,” Proc. R. Soc. London, Ser. A 315, 69–97 (1970).
[CrossRef]

Sov. Phys. Solid State (1)

L. D. Livanova, I. G. Saitkulov, and A. L. Stolov, “Summation processes for quanta in CaF2 and SrF2 single crystals activated with Tb3+ and Yb3+ ions,” Sov. Phys. Solid State 11, 750–754 (1969).

Z. Phys. (1)

A. Smakula, “Über Erregung und Entfärburg lichtelektrisch leitender Alkalihalogenide,” Z. Phys. 59, 603–614 (1930).
[CrossRef]

Other (4)

T. Moeller, “The Lanthanides,” in Comprehensive Inorganic Chemistry, J. C. Bailar, H. J. Emeleus, R. Nyholm, and A. F. Trotman-Dickenson, eds. (Pergamon Press, Oxford, 1973), Vol. 4, pp. 1–101.

K. S. Song and R. T. Williams, “Alkaline earth fluorides,” in Self-Trapped Excitons (Springer-Verlag, Berlin, 1996) pp. 96–122.

R. T. Williams and E. J. Friebele, “CaF2, SrF2, BaF2,” in Vol. 3 of CRC Handbook of Laser Science and Technology, M. J. Weber, ed. (CRC Press, Boca Raton, Florida, 1986), pp. 309–310.

W. Hayes and A. M. Stoneham, “Color centers,” in Crystals with the Fluorite Structure, W. Hayes, ed. (Oxford U. Press, London, 1974), pp. 185–280.

Cited By

OSA participates in CrossRef's Cited-By Linking service. Citing articles from OSA journals and other participating publishers are listed here.

Alert me when this article is cited.


Figures (10)

Fig. 1
Fig. 1

Schematic structure of Y-associated F- center (YFC). A sublattice of a CaF2 crystal is extracted. The YFC is composed of a fluorine ion vacancy trapping two electrons and a trivalent yttrium ion at the nearest-neighbor Ca2+ site.

Fig. 2
Fig. 2

Setup for time-resolved PL measurement with an ArF or KrF excimer laser as the excitation source.

Fig. 3
Fig. 3

Time-resolved PL spectra of (a) excimer grade (A) and (b) excimer grade (B) on excitation with an ArF excimer laser pulse. Predominant PL bands are numbered 1–5. The origins of emission band 1, STE; bands 2 and 3, Ce3+; and band 4, Eu2+. (c) Time-resolved PL spectra of the UV grade specimen. A series of emission bands originates from Tb3+. Band 5 is the most intense band. Since a series of emission bands have long lifetime of ∼5 ms, these bands are distinguishable from bands 1–4 in the time-resolved measurement.

Fig. 4
Fig. 4

Time-resolved PL spectra of (a) excimer grade (A), (b) excimer grade (B), and (c) UV grade on excitation with a KrF excimer laser pulse. Predominant PL bands are numbered 2–4. The origins of these emission bands are the same as stated in Fig. 3.

Fig. 5
Fig. 5

Log–log plots of PL intensities versus ArF laser power density. Each datum shows a luminescence band resulting from STE (solid triangle), Ce3+ (open square), Eu2+ (solid square), and Tb3+ (solid circle). Upper and lower dashed lines, slopes of 2 and 1, respectively.

Fig. 6
Fig. 6

PL intensity of band 5 observed in the UV grade specimen as a function of total ArF laser shots. Power density and repetition are 120 mJ/(cm2 pulse) and 10 Hz, respectively.

Fig. 7
Fig. 7

Optical absorption spectra induced by irradiation with 10,000 pulses of ArF excimer laser light. Dotted and dashed curves, induced absorption spectra of excimer grades (A) and (B), respectively. The characteristic 5-band spectrum traced by the solid curve were observed for the UV grade specimen.

Fig. 8
Fig. 8

Intensity of the induced absorption band resulting from the YFC as a function of the ArF laser power density. The intensity of the 2.1-eV band among the 5 bands that are due to the YFC was taken. Every datum was obtained through the irradiation of 10,000 pulses. Data were least-square-fitted with a straight line (described by the dashed line) having a slope of 1.

Fig. 9
Fig. 9

Intensity of the 2.1-eV band (due to the YFC) as a function of total ArF laser pulse shots. Every datum was obtained after the irradiation of 120 mJ/(cm2 pulse). The dashed curve was obtained by a least-square-fitting with Eq. (2) showing a first-order kinetics. Δabs(), the saturation level of the induced YFC bands, was estimated as 0.02 (cm-1).

Fig. 10
Fig. 10

Correlation between PL intensity of 541-nm band of Tb3+ and intensity of the 2.1-eV band that is due to the YFC. The dashed straight line was fitted to the data by a least-squares method. The numbers beside the dots show the total ArF laser pulses.

Tables (3)

Tables Icon

Table 1 Chemically Analyzed Impurity Contents (Mass ppm) in the Samples

Tables Icon

Table 2 Observed PL and Induced Absorption Bands

Tables Icon

Table 3 Properties of Predominant PL Bands at Room Temperature

Equations (5)

Equations on this page are rendered with MathJax. Learn more.

dN/dn=k(N0-N),
Δabs=Δabs()[1-exp(-kn)],
N·f=0.87×1017n0αW/(n02+2)2,
Tb2++hν(6.4 eV)Tb3++e-(photo),
e-(photo)+precursor of YFCYFC,

Metrics