Abstract

The authors have demonstrated white light emission of rare earth (RE)-free Mn-doped SnO-ZnO-P2O5 glass. The RE-free glass shows white light emission with a high value of quantum efficiency (QE) comparable to conventional crystalline phosphor. It is notable that the high QE value is attained for RE-free transparent glass, and the broad emission can be continuously tuned by both the amount of activator and the composition of the glass. Since this glass possesses low-melting property, we emphasize that the glass phosphor will lead to the development of a novel inorganic white-light-emitting device in combination with a solid state UV light-emitting source.

© 2011 Optical Society of America

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References

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  1. W. M. Yen, S. Shionoya, and H. Yamamoto, Phosphor Handbook, 2nd ed. (CRC, 2007).
  2. S. Nakamura, T. Mukai, and M. Senoh, Jpn. J. Appl. Phys. Lett. 30, L1998 (1991).
    [CrossRef]
  3. M. C. Schmidt, K.-C. Kim, H. Sato, N. Fellows, H. Masui, S. Nakamura, S. P. Denbaars, and J. S. Speck, Jpn. J. Appl. Phys. 46, L126 (2007).
    [CrossRef]
  4. H. Hirayama, N. Noguchi, and N. Kamata, Appl. Phys. Express 3, 032102 (2010).
    [CrossRef]
  5. T. Oto, R. G. Banal, K. Kataoka, M. Funato, and Y. Kawakami, Nat. Photon. 4, 767 (2010).
    [CrossRef]
  6. A. Wachtel, J. Electrochem. Soc. 113, 128 (1966).
    [CrossRef]
  7. K. H. Butler and C. W. Jerome, J. Electrochem. Soc. 97, 265 (1950).
    [CrossRef]
  8. R. C. Ropp and R. W. Mooney, J. Electrochem. Soc. 107, 15 (1960).
    [CrossRef]
  9. T. S. Davis, E. R. Kreidler, J. A. Parodi, and T. F. Soules, J. Lumin. 4, 48 (1971).
    [CrossRef]
  10. M. Leskelä, T. Koskentalo, and G. Blasse, J. Solid State Chem. 59, 272 (1985).
    [CrossRef]
  11. R. H. Clapp and R. J. Ginther, J. Opt. Soc. Am. 37, 355(1947).
    [CrossRef] [PubMed]
  12. H. Masai, Y. Takahashi, T. Fujiwara, S. Matsumoto, and T. Yoko, Appl. Phys. Express 3, 082102 (2010).
    [CrossRef]
  13. L. Skuja, J. Non-Cryst. Solids 149, 77 (1992).
    [CrossRef]
  14. T. Hayakawa, T. Enomoto, and M. Nogami, Jpn. J. Appl. Phys. 45, 5078 (2006).
    [CrossRef]
  15. T. Akai and K. Kadono, “Transparent white fluorescent glass,” U. S. patent WO 2007017928-A1 (Aug. 8, 2005).
  16. J. G. Hooley, “Fluorescent glass composition,” U. S. patent 2,400,147 (May 14, 1946).
  17. S. Matsumoto, N. Nakamura, and N. Wada, “Glass, coating material for light-emitting device, and light-emitting device,” U. S. patent WO 2009/088086 (Jan. 9, 2009).
  18. S. Matsumoto, Y. Osaki, and N. Nakamura, “Glass for optical device covering, glass-covered light-emitting element, and glass-covered light-emitting device,” U. S. patent WO 2008/146886 (May 29, 2008).
  19. K. H. Butler, J. Electrochem. Soc. 100, 250 (1953).
    [CrossRef]
  20. D. L. Dexter, J. Chem. Phys. 21, 836 (1953).
    [CrossRef]
  21. J. A. Duffy and M. D. Ingram, J. Non-Cryst. Solids 21, 373(1976).
    [CrossRef]
  22. J. A. Duffy and M. D. Ingram, J. Am. Chem. Soc. 93, 6448(1971).
    [CrossRef]

2010 (3)

H. Hirayama, N. Noguchi, and N. Kamata, Appl. Phys. Express 3, 032102 (2010).
[CrossRef]

T. Oto, R. G. Banal, K. Kataoka, M. Funato, and Y. Kawakami, Nat. Photon. 4, 767 (2010).
[CrossRef]

H. Masai, Y. Takahashi, T. Fujiwara, S. Matsumoto, and T. Yoko, Appl. Phys. Express 3, 082102 (2010).
[CrossRef]

2007 (1)

M. C. Schmidt, K.-C. Kim, H. Sato, N. Fellows, H. Masui, S. Nakamura, S. P. Denbaars, and J. S. Speck, Jpn. J. Appl. Phys. 46, L126 (2007).
[CrossRef]

2006 (1)

T. Hayakawa, T. Enomoto, and M. Nogami, Jpn. J. Appl. Phys. 45, 5078 (2006).
[CrossRef]

1992 (1)

L. Skuja, J. Non-Cryst. Solids 149, 77 (1992).
[CrossRef]

1991 (1)

S. Nakamura, T. Mukai, and M. Senoh, Jpn. J. Appl. Phys. Lett. 30, L1998 (1991).
[CrossRef]

1985 (1)

M. Leskelä, T. Koskentalo, and G. Blasse, J. Solid State Chem. 59, 272 (1985).
[CrossRef]

1976 (1)

J. A. Duffy and M. D. Ingram, J. Non-Cryst. Solids 21, 373(1976).
[CrossRef]

1971 (2)

J. A. Duffy and M. D. Ingram, J. Am. Chem. Soc. 93, 6448(1971).
[CrossRef]

T. S. Davis, E. R. Kreidler, J. A. Parodi, and T. F. Soules, J. Lumin. 4, 48 (1971).
[CrossRef]

1966 (1)

A. Wachtel, J. Electrochem. Soc. 113, 128 (1966).
[CrossRef]

1960 (1)

R. C. Ropp and R. W. Mooney, J. Electrochem. Soc. 107, 15 (1960).
[CrossRef]

1953 (2)

K. H. Butler, J. Electrochem. Soc. 100, 250 (1953).
[CrossRef]

D. L. Dexter, J. Chem. Phys. 21, 836 (1953).
[CrossRef]

1950 (1)

K. H. Butler and C. W. Jerome, J. Electrochem. Soc. 97, 265 (1950).
[CrossRef]

1947 (1)

Akai, T.

T. Akai and K. Kadono, “Transparent white fluorescent glass,” U. S. patent WO 2007017928-A1 (Aug. 8, 2005).

Banal, R. G.

T. Oto, R. G. Banal, K. Kataoka, M. Funato, and Y. Kawakami, Nat. Photon. 4, 767 (2010).
[CrossRef]

Blasse, G.

M. Leskelä, T. Koskentalo, and G. Blasse, J. Solid State Chem. 59, 272 (1985).
[CrossRef]

Butler, K. H.

K. H. Butler, J. Electrochem. Soc. 100, 250 (1953).
[CrossRef]

K. H. Butler and C. W. Jerome, J. Electrochem. Soc. 97, 265 (1950).
[CrossRef]

Clapp, R. H.

Davis, T. S.

T. S. Davis, E. R. Kreidler, J. A. Parodi, and T. F. Soules, J. Lumin. 4, 48 (1971).
[CrossRef]

Denbaars, S. P.

M. C. Schmidt, K.-C. Kim, H. Sato, N. Fellows, H. Masui, S. Nakamura, S. P. Denbaars, and J. S. Speck, Jpn. J. Appl. Phys. 46, L126 (2007).
[CrossRef]

Dexter, D. L.

D. L. Dexter, J. Chem. Phys. 21, 836 (1953).
[CrossRef]

Duffy, J. A.

J. A. Duffy and M. D. Ingram, J. Non-Cryst. Solids 21, 373(1976).
[CrossRef]

J. A. Duffy and M. D. Ingram, J. Am. Chem. Soc. 93, 6448(1971).
[CrossRef]

Enomoto, T.

T. Hayakawa, T. Enomoto, and M. Nogami, Jpn. J. Appl. Phys. 45, 5078 (2006).
[CrossRef]

Fellows, N.

M. C. Schmidt, K.-C. Kim, H. Sato, N. Fellows, H. Masui, S. Nakamura, S. P. Denbaars, and J. S. Speck, Jpn. J. Appl. Phys. 46, L126 (2007).
[CrossRef]

Fujiwara, T.

H. Masai, Y. Takahashi, T. Fujiwara, S. Matsumoto, and T. Yoko, Appl. Phys. Express 3, 082102 (2010).
[CrossRef]

Funato, M.

T. Oto, R. G. Banal, K. Kataoka, M. Funato, and Y. Kawakami, Nat. Photon. 4, 767 (2010).
[CrossRef]

Ginther, R. J.

Hayakawa, T.

T. Hayakawa, T. Enomoto, and M. Nogami, Jpn. J. Appl. Phys. 45, 5078 (2006).
[CrossRef]

Hirayama, H.

H. Hirayama, N. Noguchi, and N. Kamata, Appl. Phys. Express 3, 032102 (2010).
[CrossRef]

Hooley, J. G.

J. G. Hooley, “Fluorescent glass composition,” U. S. patent 2,400,147 (May 14, 1946).

Ingram, M. D.

J. A. Duffy and M. D. Ingram, J. Non-Cryst. Solids 21, 373(1976).
[CrossRef]

J. A. Duffy and M. D. Ingram, J. Am. Chem. Soc. 93, 6448(1971).
[CrossRef]

Jerome, C. W.

K. H. Butler and C. W. Jerome, J. Electrochem. Soc. 97, 265 (1950).
[CrossRef]

Kadono, K.

T. Akai and K. Kadono, “Transparent white fluorescent glass,” U. S. patent WO 2007017928-A1 (Aug. 8, 2005).

Kamata, N.

H. Hirayama, N. Noguchi, and N. Kamata, Appl. Phys. Express 3, 032102 (2010).
[CrossRef]

Kataoka, K.

T. Oto, R. G. Banal, K. Kataoka, M. Funato, and Y. Kawakami, Nat. Photon. 4, 767 (2010).
[CrossRef]

Kawakami, Y.

T. Oto, R. G. Banal, K. Kataoka, M. Funato, and Y. Kawakami, Nat. Photon. 4, 767 (2010).
[CrossRef]

Kim, K.-C.

M. C. Schmidt, K.-C. Kim, H. Sato, N. Fellows, H. Masui, S. Nakamura, S. P. Denbaars, and J. S. Speck, Jpn. J. Appl. Phys. 46, L126 (2007).
[CrossRef]

Koskentalo, T.

M. Leskelä, T. Koskentalo, and G. Blasse, J. Solid State Chem. 59, 272 (1985).
[CrossRef]

Kreidler, E. R.

T. S. Davis, E. R. Kreidler, J. A. Parodi, and T. F. Soules, J. Lumin. 4, 48 (1971).
[CrossRef]

Leskelä, M.

M. Leskelä, T. Koskentalo, and G. Blasse, J. Solid State Chem. 59, 272 (1985).
[CrossRef]

Masai, H.

H. Masai, Y. Takahashi, T. Fujiwara, S. Matsumoto, and T. Yoko, Appl. Phys. Express 3, 082102 (2010).
[CrossRef]

Masui, H.

M. C. Schmidt, K.-C. Kim, H. Sato, N. Fellows, H. Masui, S. Nakamura, S. P. Denbaars, and J. S. Speck, Jpn. J. Appl. Phys. 46, L126 (2007).
[CrossRef]

Matsumoto, S.

H. Masai, Y. Takahashi, T. Fujiwara, S. Matsumoto, and T. Yoko, Appl. Phys. Express 3, 082102 (2010).
[CrossRef]

S. Matsumoto, Y. Osaki, and N. Nakamura, “Glass for optical device covering, glass-covered light-emitting element, and glass-covered light-emitting device,” U. S. patent WO 2008/146886 (May 29, 2008).

S. Matsumoto, N. Nakamura, and N. Wada, “Glass, coating material for light-emitting device, and light-emitting device,” U. S. patent WO 2009/088086 (Jan. 9, 2009).

Mooney, R. W.

R. C. Ropp and R. W. Mooney, J. Electrochem. Soc. 107, 15 (1960).
[CrossRef]

Mukai, T.

S. Nakamura, T. Mukai, and M. Senoh, Jpn. J. Appl. Phys. Lett. 30, L1998 (1991).
[CrossRef]

Nakamura, N.

S. Matsumoto, N. Nakamura, and N. Wada, “Glass, coating material for light-emitting device, and light-emitting device,” U. S. patent WO 2009/088086 (Jan. 9, 2009).

S. Matsumoto, Y. Osaki, and N. Nakamura, “Glass for optical device covering, glass-covered light-emitting element, and glass-covered light-emitting device,” U. S. patent WO 2008/146886 (May 29, 2008).

Nakamura, S.

M. C. Schmidt, K.-C. Kim, H. Sato, N. Fellows, H. Masui, S. Nakamura, S. P. Denbaars, and J. S. Speck, Jpn. J. Appl. Phys. 46, L126 (2007).
[CrossRef]

S. Nakamura, T. Mukai, and M. Senoh, Jpn. J. Appl. Phys. Lett. 30, L1998 (1991).
[CrossRef]

Nogami, M.

T. Hayakawa, T. Enomoto, and M. Nogami, Jpn. J. Appl. Phys. 45, 5078 (2006).
[CrossRef]

Noguchi, N.

H. Hirayama, N. Noguchi, and N. Kamata, Appl. Phys. Express 3, 032102 (2010).
[CrossRef]

Osaki, Y.

S. Matsumoto, Y. Osaki, and N. Nakamura, “Glass for optical device covering, glass-covered light-emitting element, and glass-covered light-emitting device,” U. S. patent WO 2008/146886 (May 29, 2008).

Oto, T.

T. Oto, R. G. Banal, K. Kataoka, M. Funato, and Y. Kawakami, Nat. Photon. 4, 767 (2010).
[CrossRef]

Parodi, J. A.

T. S. Davis, E. R. Kreidler, J. A. Parodi, and T. F. Soules, J. Lumin. 4, 48 (1971).
[CrossRef]

Ropp, R. C.

R. C. Ropp and R. W. Mooney, J. Electrochem. Soc. 107, 15 (1960).
[CrossRef]

Sato, H.

M. C. Schmidt, K.-C. Kim, H. Sato, N. Fellows, H. Masui, S. Nakamura, S. P. Denbaars, and J. S. Speck, Jpn. J. Appl. Phys. 46, L126 (2007).
[CrossRef]

Schmidt, M. C.

M. C. Schmidt, K.-C. Kim, H. Sato, N. Fellows, H. Masui, S. Nakamura, S. P. Denbaars, and J. S. Speck, Jpn. J. Appl. Phys. 46, L126 (2007).
[CrossRef]

Senoh, M.

S. Nakamura, T. Mukai, and M. Senoh, Jpn. J. Appl. Phys. Lett. 30, L1998 (1991).
[CrossRef]

Shionoya, S.

W. M. Yen, S. Shionoya, and H. Yamamoto, Phosphor Handbook, 2nd ed. (CRC, 2007).

Skuja, L.

L. Skuja, J. Non-Cryst. Solids 149, 77 (1992).
[CrossRef]

Soules, T. F.

T. S. Davis, E. R. Kreidler, J. A. Parodi, and T. F. Soules, J. Lumin. 4, 48 (1971).
[CrossRef]

Speck, J. S.

M. C. Schmidt, K.-C. Kim, H. Sato, N. Fellows, H. Masui, S. Nakamura, S. P. Denbaars, and J. S. Speck, Jpn. J. Appl. Phys. 46, L126 (2007).
[CrossRef]

Takahashi, Y.

H. Masai, Y. Takahashi, T. Fujiwara, S. Matsumoto, and T. Yoko, Appl. Phys. Express 3, 082102 (2010).
[CrossRef]

Wachtel, A.

A. Wachtel, J. Electrochem. Soc. 113, 128 (1966).
[CrossRef]

Wada, N.

S. Matsumoto, N. Nakamura, and N. Wada, “Glass, coating material for light-emitting device, and light-emitting device,” U. S. patent WO 2009/088086 (Jan. 9, 2009).

Yamamoto, H.

W. M. Yen, S. Shionoya, and H. Yamamoto, Phosphor Handbook, 2nd ed. (CRC, 2007).

Yen, W. M.

W. M. Yen, S. Shionoya, and H. Yamamoto, Phosphor Handbook, 2nd ed. (CRC, 2007).

Yoko, T.

H. Masai, Y. Takahashi, T. Fujiwara, S. Matsumoto, and T. Yoko, Appl. Phys. Express 3, 082102 (2010).
[CrossRef]

Appl. Phys. Express (2)

H. Hirayama, N. Noguchi, and N. Kamata, Appl. Phys. Express 3, 032102 (2010).
[CrossRef]

H. Masai, Y. Takahashi, T. Fujiwara, S. Matsumoto, and T. Yoko, Appl. Phys. Express 3, 082102 (2010).
[CrossRef]

J. Am. Chem. Soc. (1)

J. A. Duffy and M. D. Ingram, J. Am. Chem. Soc. 93, 6448(1971).
[CrossRef]

J. Chem. Phys. (1)

D. L. Dexter, J. Chem. Phys. 21, 836 (1953).
[CrossRef]

J. Electrochem. Soc. (4)

K. H. Butler, J. Electrochem. Soc. 100, 250 (1953).
[CrossRef]

A. Wachtel, J. Electrochem. Soc. 113, 128 (1966).
[CrossRef]

K. H. Butler and C. W. Jerome, J. Electrochem. Soc. 97, 265 (1950).
[CrossRef]

R. C. Ropp and R. W. Mooney, J. Electrochem. Soc. 107, 15 (1960).
[CrossRef]

J. Lumin. (1)

T. S. Davis, E. R. Kreidler, J. A. Parodi, and T. F. Soules, J. Lumin. 4, 48 (1971).
[CrossRef]

J. Non-Cryst. Solids (2)

J. A. Duffy and M. D. Ingram, J. Non-Cryst. Solids 21, 373(1976).
[CrossRef]

L. Skuja, J. Non-Cryst. Solids 149, 77 (1992).
[CrossRef]

J. Opt. Soc. Am. (1)

J. Solid State Chem. (1)

M. Leskelä, T. Koskentalo, and G. Blasse, J. Solid State Chem. 59, 272 (1985).
[CrossRef]

Jpn. J. Appl. Phys. (2)

T. Hayakawa, T. Enomoto, and M. Nogami, Jpn. J. Appl. Phys. 45, 5078 (2006).
[CrossRef]

M. C. Schmidt, K.-C. Kim, H. Sato, N. Fellows, H. Masui, S. Nakamura, S. P. Denbaars, and J. S. Speck, Jpn. J. Appl. Phys. 46, L126 (2007).
[CrossRef]

Jpn. J. Appl. Phys. Lett. (1)

S. Nakamura, T. Mukai, and M. Senoh, Jpn. J. Appl. Phys. Lett. 30, L1998 (1991).
[CrossRef]

Nat. Photon. (1)

T. Oto, R. G. Banal, K. Kataoka, M. Funato, and Y. Kawakami, Nat. Photon. 4, 767 (2010).
[CrossRef]

Other (5)

W. M. Yen, S. Shionoya, and H. Yamamoto, Phosphor Handbook, 2nd ed. (CRC, 2007).

T. Akai and K. Kadono, “Transparent white fluorescent glass,” U. S. patent WO 2007017928-A1 (Aug. 8, 2005).

J. G. Hooley, “Fluorescent glass composition,” U. S. patent 2,400,147 (May 14, 1946).

S. Matsumoto, N. Nakamura, and N. Wada, “Glass, coating material for light-emitting device, and light-emitting device,” U. S. patent WO 2009/088086 (Jan. 9, 2009).

S. Matsumoto, Y. Osaki, and N. Nakamura, “Glass for optical device covering, glass-covered light-emitting element, and glass-covered light-emitting device,” U. S. patent WO 2008/146886 (May 29, 2008).

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Figures (3)

Fig. 1
Fig. 1

Correlation between PL intensity excited by 4.88 eV and the amount of Mn in the x MnO - 2.5 SnO - 57.5 ZnO - 40 P 2 O 5 glasses.

Fig. 2
Fig. 2

PL and PLE spectra of 0.5 MnO - 2.5 SnO - y ZnO - ( 97.5 - y ) P 2 O 5 glasses.

Fig. 3
Fig. 3

Chromatic coordination mapping of the SnO - ZnO - P 2 O 5 glasses excited by the photon energy of 4.88 eV ( 254 nm ). Black circles: x MnO - 2.5 SnO - 57.5 ZnO - 40 P 2 O 5 . Green squares: 0.5 MnO - 2.5 SnO - ( 97.5 - y ) ZnO - y P 2 O 5 . Blue triangles: 0.25 MnO - 2.5 SnO - ( 97.5 - z ) ZnO - z P 2 O 5 . Inset shows photograph of the glass phosphors ( x = 0 , 0.7, 2.0) with and without UV light ( 254 nm ).

Tables (1)

Tables Icon

Table 1 Chemical Composition of the MnO - SnO - ZnO - P 2 O 5 Glasses and the NQE a

Equations (1)

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

NQE = P g Δ E s / P s Δ E g ,

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