Abstract

Photochemical reactions in 10 GeO2 –90 SiO2 glass induced by irradiation with excimer lasers (KrF, 5.0 eV, XeCl, 4.0 eV) and a Hg lamp (4.9 eV) were examined. The irradiation with excimer lasers generated two types of paramagnetic defect, an electron-trapped center associated with fourfold coordinated Ge ions and a self-trapped hole center on bridging oxygen. Taking the optical band gap (~7.1 eV) of the glass obtained in this work and the power density of laser pulses [10–90 mJ/(cm2 pulse), pulse duration 20 ns] into account, we concluded that these centers were formed by band-to-band excitation by two-photon absorption process. On the other hand, the lamp illumination (~16 mW/cm2) caused the formation of Ge E′ centers from preexisting oxygen-vacancy-type defects by the one-photon absorption process. These two kinds of reaction proceed independently, depending on the power densities of UV beams, at least in our experimental condition.

© 1995 Optical Society of America

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  1. R. M. Atkins, V. Mizurahi, Electron. Lett. 28, 1743 (1992).
    [CrossRef]
  2. H. Hosono, Y. Abe, D. L. Kinser, R. A. Weeks, K. Muta, H. Kawazoe, Phys. Rev. B 46, 11445 (1992).
    [CrossRef]
  3. T. E. Tsai, E. J. Friebele, M. Rajaram, S. Mukhapadhyay, Appl. Phys. Lett. 64, 1481 (1994).
    [CrossRef]
  4. R. M. Atkins, V. Mizrahi, T. Erdogan, Electron. Lett. 29, 385 (1993).
    [CrossRef]
  5. C. G. Askins, T. E. Tsai, G. M. Williams, M. A. Putnum, M. Bashkansky, E. J. Friebele, Opt. Lett. 17, 833 (1992).
    [CrossRef] [PubMed]
  6. G. Meltz, W. W. Morey, Proc. Soc. Photo-Opt. Instrum. Eng. 1516, 185 (1991).
  7. H. Imai, K. Arai, H. Imagawa, H. Hosono, Y. Abe, Phys. Rev. B 38, 12772 (1988).
    [CrossRef]
  8. J. Nishii, H. Yamanaka, H. Hosono, H. Kawazoe, Appl. Phys. Lett. 64, 282 (1994).
    [CrossRef]
  9. H. Kawazoe, J. Non-Cryst. Solids 71, 231 (1985).
    [CrossRef]
  10. T. E. Tsai, D. L. Griscom, E. J. Friebele, Diffusion Defect Data 53–54, 469 (1987).
    [CrossRef]
  11. E. J. Friebele, D. L. Griscom, Mat. Res. Soc. Symp. Proc. 61, 319 (1985).
    [CrossRef]
  12. T. E. Tsai, D. L. Griscom, E. J. Friebele, J. Appl. Phys. 62, 2264 (1987).
    [CrossRef]
  13. D. L. Griscom, Phys. Rev. B 40, 4224 (1989).
    [CrossRef]
  14. Z. A. Weinberg, G. W. Rubloff, E. Bassous, Phys. Rev. B 19, 3107 (1979).
    [CrossRef]
  15. N. M. Ravindra, R. A. Weeks, D. L. Kinser, Phys. Rev. B 36, 6132 (1987).
    [CrossRef]
  16. The concentration of induced STH is less than that of induced GEC. This difference is considered to be the thermal stability of STH and GEC, i.e., STH is stable at low temperature at 77 K but is unstable at room temperature,13 whereas GEC is stable above 250 °C.11
  17. P. St. Russell, D. P. Hand, Opt. Lett. 15, 102 (1990).
    [CrossRef] [PubMed]

1994 (2)

T. E. Tsai, E. J. Friebele, M. Rajaram, S. Mukhapadhyay, Appl. Phys. Lett. 64, 1481 (1994).
[CrossRef]

J. Nishii, H. Yamanaka, H. Hosono, H. Kawazoe, Appl. Phys. Lett. 64, 282 (1994).
[CrossRef]

1993 (1)

R. M. Atkins, V. Mizrahi, T. Erdogan, Electron. Lett. 29, 385 (1993).
[CrossRef]

1992 (3)

C. G. Askins, T. E. Tsai, G. M. Williams, M. A. Putnum, M. Bashkansky, E. J. Friebele, Opt. Lett. 17, 833 (1992).
[CrossRef] [PubMed]

R. M. Atkins, V. Mizurahi, Electron. Lett. 28, 1743 (1992).
[CrossRef]

H. Hosono, Y. Abe, D. L. Kinser, R. A. Weeks, K. Muta, H. Kawazoe, Phys. Rev. B 46, 11445 (1992).
[CrossRef]

1991 (1)

G. Meltz, W. W. Morey, Proc. Soc. Photo-Opt. Instrum. Eng. 1516, 185 (1991).

1990 (1)

1989 (1)

D. L. Griscom, Phys. Rev. B 40, 4224 (1989).
[CrossRef]

1988 (1)

H. Imai, K. Arai, H. Imagawa, H. Hosono, Y. Abe, Phys. Rev. B 38, 12772 (1988).
[CrossRef]

1987 (3)

T. E. Tsai, D. L. Griscom, E. J. Friebele, Diffusion Defect Data 53–54, 469 (1987).
[CrossRef]

T. E. Tsai, D. L. Griscom, E. J. Friebele, J. Appl. Phys. 62, 2264 (1987).
[CrossRef]

N. M. Ravindra, R. A. Weeks, D. L. Kinser, Phys. Rev. B 36, 6132 (1987).
[CrossRef]

1985 (2)

E. J. Friebele, D. L. Griscom, Mat. Res. Soc. Symp. Proc. 61, 319 (1985).
[CrossRef]

H. Kawazoe, J. Non-Cryst. Solids 71, 231 (1985).
[CrossRef]

1979 (1)

Z. A. Weinberg, G. W. Rubloff, E. Bassous, Phys. Rev. B 19, 3107 (1979).
[CrossRef]

Abe, Y.

H. Hosono, Y. Abe, D. L. Kinser, R. A. Weeks, K. Muta, H. Kawazoe, Phys. Rev. B 46, 11445 (1992).
[CrossRef]

H. Imai, K. Arai, H. Imagawa, H. Hosono, Y. Abe, Phys. Rev. B 38, 12772 (1988).
[CrossRef]

Arai, K.

H. Imai, K. Arai, H. Imagawa, H. Hosono, Y. Abe, Phys. Rev. B 38, 12772 (1988).
[CrossRef]

Askins, C. G.

Atkins, R. M.

R. M. Atkins, V. Mizrahi, T. Erdogan, Electron. Lett. 29, 385 (1993).
[CrossRef]

R. M. Atkins, V. Mizurahi, Electron. Lett. 28, 1743 (1992).
[CrossRef]

Bashkansky, M.

Bassous, E.

Z. A. Weinberg, G. W. Rubloff, E. Bassous, Phys. Rev. B 19, 3107 (1979).
[CrossRef]

Erdogan, T.

R. M. Atkins, V. Mizrahi, T. Erdogan, Electron. Lett. 29, 385 (1993).
[CrossRef]

Friebele, E. J.

T. E. Tsai, E. J. Friebele, M. Rajaram, S. Mukhapadhyay, Appl. Phys. Lett. 64, 1481 (1994).
[CrossRef]

C. G. Askins, T. E. Tsai, G. M. Williams, M. A. Putnum, M. Bashkansky, E. J. Friebele, Opt. Lett. 17, 833 (1992).
[CrossRef] [PubMed]

T. E. Tsai, D. L. Griscom, E. J. Friebele, Diffusion Defect Data 53–54, 469 (1987).
[CrossRef]

T. E. Tsai, D. L. Griscom, E. J. Friebele, J. Appl. Phys. 62, 2264 (1987).
[CrossRef]

E. J. Friebele, D. L. Griscom, Mat. Res. Soc. Symp. Proc. 61, 319 (1985).
[CrossRef]

Griscom, D. L.

D. L. Griscom, Phys. Rev. B 40, 4224 (1989).
[CrossRef]

T. E. Tsai, D. L. Griscom, E. J. Friebele, J. Appl. Phys. 62, 2264 (1987).
[CrossRef]

T. E. Tsai, D. L. Griscom, E. J. Friebele, Diffusion Defect Data 53–54, 469 (1987).
[CrossRef]

E. J. Friebele, D. L. Griscom, Mat. Res. Soc. Symp. Proc. 61, 319 (1985).
[CrossRef]

Hand, D. P.

Hosono, H.

J. Nishii, H. Yamanaka, H. Hosono, H. Kawazoe, Appl. Phys. Lett. 64, 282 (1994).
[CrossRef]

H. Hosono, Y. Abe, D. L. Kinser, R. A. Weeks, K. Muta, H. Kawazoe, Phys. Rev. B 46, 11445 (1992).
[CrossRef]

H. Imai, K. Arai, H. Imagawa, H. Hosono, Y. Abe, Phys. Rev. B 38, 12772 (1988).
[CrossRef]

Imagawa, H.

H. Imai, K. Arai, H. Imagawa, H. Hosono, Y. Abe, Phys. Rev. B 38, 12772 (1988).
[CrossRef]

Imai, H.

H. Imai, K. Arai, H. Imagawa, H. Hosono, Y. Abe, Phys. Rev. B 38, 12772 (1988).
[CrossRef]

Kawazoe, H.

J. Nishii, H. Yamanaka, H. Hosono, H. Kawazoe, Appl. Phys. Lett. 64, 282 (1994).
[CrossRef]

H. Hosono, Y. Abe, D. L. Kinser, R. A. Weeks, K. Muta, H. Kawazoe, Phys. Rev. B 46, 11445 (1992).
[CrossRef]

H. Kawazoe, J. Non-Cryst. Solids 71, 231 (1985).
[CrossRef]

Kinser, D. L.

H. Hosono, Y. Abe, D. L. Kinser, R. A. Weeks, K. Muta, H. Kawazoe, Phys. Rev. B 46, 11445 (1992).
[CrossRef]

N. M. Ravindra, R. A. Weeks, D. L. Kinser, Phys. Rev. B 36, 6132 (1987).
[CrossRef]

Meltz, G.

G. Meltz, W. W. Morey, Proc. Soc. Photo-Opt. Instrum. Eng. 1516, 185 (1991).

Mizrahi, V.

R. M. Atkins, V. Mizrahi, T. Erdogan, Electron. Lett. 29, 385 (1993).
[CrossRef]

Mizurahi, V.

R. M. Atkins, V. Mizurahi, Electron. Lett. 28, 1743 (1992).
[CrossRef]

Morey, W. W.

G. Meltz, W. W. Morey, Proc. Soc. Photo-Opt. Instrum. Eng. 1516, 185 (1991).

Mukhapadhyay, S.

T. E. Tsai, E. J. Friebele, M. Rajaram, S. Mukhapadhyay, Appl. Phys. Lett. 64, 1481 (1994).
[CrossRef]

Muta, K.

H. Hosono, Y. Abe, D. L. Kinser, R. A. Weeks, K. Muta, H. Kawazoe, Phys. Rev. B 46, 11445 (1992).
[CrossRef]

Nishii, J.

J. Nishii, H. Yamanaka, H. Hosono, H. Kawazoe, Appl. Phys. Lett. 64, 282 (1994).
[CrossRef]

Putnum, M. A.

Rajaram, M.

T. E. Tsai, E. J. Friebele, M. Rajaram, S. Mukhapadhyay, Appl. Phys. Lett. 64, 1481 (1994).
[CrossRef]

Ravindra, N. M.

N. M. Ravindra, R. A. Weeks, D. L. Kinser, Phys. Rev. B 36, 6132 (1987).
[CrossRef]

Rubloff, G. W.

Z. A. Weinberg, G. W. Rubloff, E. Bassous, Phys. Rev. B 19, 3107 (1979).
[CrossRef]

Russell, P. St.

Tsai, T. E.

T. E. Tsai, E. J. Friebele, M. Rajaram, S. Mukhapadhyay, Appl. Phys. Lett. 64, 1481 (1994).
[CrossRef]

C. G. Askins, T. E. Tsai, G. M. Williams, M. A. Putnum, M. Bashkansky, E. J. Friebele, Opt. Lett. 17, 833 (1992).
[CrossRef] [PubMed]

T. E. Tsai, D. L. Griscom, E. J. Friebele, Diffusion Defect Data 53–54, 469 (1987).
[CrossRef]

T. E. Tsai, D. L. Griscom, E. J. Friebele, J. Appl. Phys. 62, 2264 (1987).
[CrossRef]

Weeks, R. A.

H. Hosono, Y. Abe, D. L. Kinser, R. A. Weeks, K. Muta, H. Kawazoe, Phys. Rev. B 46, 11445 (1992).
[CrossRef]

N. M. Ravindra, R. A. Weeks, D. L. Kinser, Phys. Rev. B 36, 6132 (1987).
[CrossRef]

Weinberg, Z. A.

Z. A. Weinberg, G. W. Rubloff, E. Bassous, Phys. Rev. B 19, 3107 (1979).
[CrossRef]

Williams, G. M.

Yamanaka, H.

J. Nishii, H. Yamanaka, H. Hosono, H. Kawazoe, Appl. Phys. Lett. 64, 282 (1994).
[CrossRef]

Appl. Phys. Lett. (2)

T. E. Tsai, E. J. Friebele, M. Rajaram, S. Mukhapadhyay, Appl. Phys. Lett. 64, 1481 (1994).
[CrossRef]

J. Nishii, H. Yamanaka, H. Hosono, H. Kawazoe, Appl. Phys. Lett. 64, 282 (1994).
[CrossRef]

Diffusion Defect Data (1)

T. E. Tsai, D. L. Griscom, E. J. Friebele, Diffusion Defect Data 53–54, 469 (1987).
[CrossRef]

Electron. Lett. (2)

R. M. Atkins, V. Mizurahi, Electron. Lett. 28, 1743 (1992).
[CrossRef]

R. M. Atkins, V. Mizrahi, T. Erdogan, Electron. Lett. 29, 385 (1993).
[CrossRef]

J. Appl. Phys. (1)

T. E. Tsai, D. L. Griscom, E. J. Friebele, J. Appl. Phys. 62, 2264 (1987).
[CrossRef]

J. Non-Cryst. Solids (1)

H. Kawazoe, J. Non-Cryst. Solids 71, 231 (1985).
[CrossRef]

Mat. Res. Soc. Symp. Proc. (1)

E. J. Friebele, D. L. Griscom, Mat. Res. Soc. Symp. Proc. 61, 319 (1985).
[CrossRef]

Opt. Lett. (2)

Phys. Rev. B (5)

H. Hosono, Y. Abe, D. L. Kinser, R. A. Weeks, K. Muta, H. Kawazoe, Phys. Rev. B 46, 11445 (1992).
[CrossRef]

H. Imai, K. Arai, H. Imagawa, H. Hosono, Y. Abe, Phys. Rev. B 38, 12772 (1988).
[CrossRef]

D. L. Griscom, Phys. Rev. B 40, 4224 (1989).
[CrossRef]

Z. A. Weinberg, G. W. Rubloff, E. Bassous, Phys. Rev. B 19, 3107 (1979).
[CrossRef]

N. M. Ravindra, R. A. Weeks, D. L. Kinser, Phys. Rev. B 36, 6132 (1987).
[CrossRef]

Proc. Soc. Photo-Opt. Instrum. Eng. (1)

G. Meltz, W. W. Morey, Proc. Soc. Photo-Opt. Instrum. Eng. 1516, 185 (1991).

Other (1)

The concentration of induced STH is less than that of induced GEC. This difference is considered to be the thermal stability of STH and GEC, i.e., STH is stable at low temperature at 77 K but is unstable at room temperature,13 whereas GEC is stable above 250 °C.11

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Figures (4)

Fig. 1
Fig. 1

Absorption spectra of 10 GeO2 –90 SiO2 glasses. (a) As polished; after illumination with (b) Hg lamp radiation (140 h), (c) KrF laser pulses (60 shots), (d) Hg lamp (140 h) → KrF laser pulses (60 shots). The inset shows the difference spectra of the specimens before and after (e) illumination with Hg lamp radiation (140 h) and (f ) irradiation with Hg lamp radiation (140 h) followed by KrF laser pulses (60 shots). (g) Difference spectrum between curves (e) and (f). The difference spectrum before and after irradiation with only KrF laser pulses (60 shots) is represented by curve (h).

Fig. 2
Fig. 2

ESR spectra of 10 GeO2 –90 SiO2 glasses (a) after illumination of Hg lamp radiation (140 h) and (b) subsequent irradiation with Hg lamp radiation (140 h) followed by KrF laser pulses (60 shots). Spectrometer gain was kept constant for all the measurements.

Fig. 3
Fig. 3

VUV absorption spectra of (a) 5 GeO2 –95 SiO2 thin glass film (3.8 μm thick) deposited onto the SiO2 substrate [curve (a)] and the SiO2 substrate (1 mm thick) [curve (b)]. The film was annealed at 450 °C for several hours in air before the measurement. The inset is a Tauc plot for the thin film.

Fig. 4
Fig. 4

Absorption spectra of 10 GeO2 –90 SiO2 glasses before [curve (a)] and after [curve (b)] irradiation with XeCl laser pulses (5 × 104 shots). Curve (c) is the difference spectra between curves (a) and (b).

Equations (2)

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Ge - Ge ( or Ge - Si ) Ge E + GeO 3 + ( or SiO 3 + ) + e - .
Ge 4 + ( fourfold coordinated ) + O 2 - ( bridging oxygen ) GEC + STH .

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