Abstract

The reverse saturable absorption and the optical-limiting response of metal phthalocyanines can be enhanced by use of the heavy-atom effect. Phthalocyanines containing heavy-metal atoms, such as In, Sn, and Pb, show a nearly factor-of-2 enhancement in the ratio of effective excited-state to ground-state absorption cross sections compared with those containing lighter atoms, such as Al and Si. In an f/8 optical geometry, homogeneous solutions of heavy-metal phthalocyanines, at 30% linear transmission, limit 8-ns 532-nm laser pulses to ≤ 3 μJ (the energy for 50% probability of eye damage) for incident energies as high as 800 μJ.

© 1994 Optical Society of America

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    [CrossRef]
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    [CrossRef]
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    [CrossRef]
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    [CrossRef]
  14. P. A. Miles, “‘Bottleneck’ optical limiters—the optimal use of excited-state absorbers,” Appl. Opt. (to be published).

1993

J. S. Shirk, R. G. S. Pong, F. J. Bartoli, A. W. Snow, Appl. Phys. Lett 63, 1880 (1993).
[CrossRef]

1992

L. W. Tutt, A. Kost, Nature (London) 356, 225 (1992).
[CrossRef]

T. H. Wie, D. J. Hagan, M. J. Sence, E. W. Van Stryland, J. W. Perry, D. R. Coulter, Appl. Phys. B 54, 46 (1992).
[CrossRef]

1991

J. W. Arbogast, A. P. Darmanyan, C. S. Foote, Y. Rubin, F. N. Diederich, M. Alvarez, S. J. Anz, R. L. Whetten, J. Phys. Chem. 1991, 11 (1991).
[CrossRef]

1990

1989

D. R. Coulter, V. M. Miskowski, J. W. Perry, T. H. Wie, E. W. Van Stryland, D. J. Hagan, Proc. Soc. Photo-Opt. Instrum. Eng. 1105, 42 (1989).

R. C. Hoffman, K. A. Stetyick, R. S. Potember, D. G. McLean, J. Opt. Soc. Am. B 6, 772 (1989).
[CrossRef]

1988

P. A. Firey, W. E. Ford, J. R. Sounik, M. E. Kenney, M. A. Rodgers, J. Am. Chem. Soc. 110, 7626 (1988).
[CrossRef]

1985

W. Blau, H. Byrne, W. M. Dennis, J. M. Kelly, Opt. Commun. 56, 25 (1985).
[CrossRef]

1983

T. Ohno, S. Kato, A. Yamada, T. Tanno, J. Phys. Chem. 87, 775 (1983).
[CrossRef]

1980

J. H. Brannon, D. Magde, J. Am. Chem. Soc. 102, 62 (1980).
[CrossRef]

1967

J. N. Esposito, L. E. Sutton, M. E. Kenney, Inorg. Chem. 6, 1116 (1967).
[CrossRef]

C. R. Guiliano, L. D. Hess, IEEE J. Quantum Electron. QE-3, 338 (1967).

Alvarez, M.

J. W. Arbogast, A. P. Darmanyan, C. S. Foote, Y. Rubin, F. N. Diederich, M. Alvarez, S. J. Anz, R. L. Whetten, J. Phys. Chem. 1991, 11 (1991).
[CrossRef]

Anz, S. J.

J. W. Arbogast, A. P. Darmanyan, C. S. Foote, Y. Rubin, F. N. Diederich, M. Alvarez, S. J. Anz, R. L. Whetten, J. Phys. Chem. 1991, 11 (1991).
[CrossRef]

Arbogast, J. W.

J. W. Arbogast, A. P. Darmanyan, C. S. Foote, Y. Rubin, F. N. Diederich, M. Alvarez, S. J. Anz, R. L. Whetten, J. Phys. Chem. 1991, 11 (1991).
[CrossRef]

Bartoli, F. J.

J. S. Shirk, R. G. S. Pong, F. J. Bartoli, A. W. Snow, Appl. Phys. Lett 63, 1880 (1993).
[CrossRef]

Blau, W.

W. Blau, H. Byrne, W. M. Dennis, J. M. Kelly, Opt. Commun. 56, 25 (1985).
[CrossRef]

Brannon, J. H.

J. H. Brannon, D. Magde, J. Am. Chem. Soc. 102, 62 (1980).
[CrossRef]

Byrne, H.

W. Blau, H. Byrne, W. M. Dennis, J. M. Kelly, Opt. Commun. 56, 25 (1985).
[CrossRef]

Coulter, D. R.

T. H. Wie, D. J. Hagan, M. J. Sence, E. W. Van Stryland, J. W. Perry, D. R. Coulter, Appl. Phys. B 54, 46 (1992).
[CrossRef]

D. R. Coulter, V. M. Miskowski, J. W. Perry, T. H. Wie, E. W. Van Stryland, D. J. Hagan, Proc. Soc. Photo-Opt. Instrum. Eng. 1105, 42 (1989).

Darmanyan, A. P.

J. W. Arbogast, A. P. Darmanyan, C. S. Foote, Y. Rubin, F. N. Diederich, M. Alvarez, S. J. Anz, R. L. Whetten, J. Phys. Chem. 1991, 11 (1991).
[CrossRef]

Dennis, W. M.

W. Blau, H. Byrne, W. M. Dennis, J. M. Kelly, Opt. Commun. 56, 25 (1985).
[CrossRef]

Diederich, F. N.

J. W. Arbogast, A. P. Darmanyan, C. S. Foote, Y. Rubin, F. N. Diederich, M. Alvarez, S. J. Anz, R. L. Whetten, J. Phys. Chem. 1991, 11 (1991).
[CrossRef]

Esposito, J. N.

J. N. Esposito, L. E. Sutton, M. E. Kenney, Inorg. Chem. 6, 1116 (1967).
[CrossRef]

Firey, P. A.

P. A. Firey, W. E. Ford, J. R. Sounik, M. E. Kenney, M. A. Rodgers, J. Am. Chem. Soc. 110, 7626 (1988).
[CrossRef]

Foote, C. S.

J. W. Arbogast, A. P. Darmanyan, C. S. Foote, Y. Rubin, F. N. Diederich, M. Alvarez, S. J. Anz, R. L. Whetten, J. Phys. Chem. 1991, 11 (1991).
[CrossRef]

Ford, W. E.

P. A. Firey, W. E. Ford, J. R. Sounik, M. E. Kenney, M. A. Rodgers, J. Am. Chem. Soc. 110, 7626 (1988).
[CrossRef]

Guiliano, C. R.

C. R. Guiliano, L. D. Hess, IEEE J. Quantum Electron. QE-3, 338 (1967).

Hagan, D. J.

T. H. Wie, D. J. Hagan, M. J. Sence, E. W. Van Stryland, J. W. Perry, D. R. Coulter, Appl. Phys. B 54, 46 (1992).
[CrossRef]

D. R. Coulter, V. M. Miskowski, J. W. Perry, T. H. Wie, E. W. Van Stryland, D. J. Hagan, Proc. Soc. Photo-Opt. Instrum. Eng. 1105, 42 (1989).

Hess, L. D.

C. R. Guiliano, L. D. Hess, IEEE J. Quantum Electron. QE-3, 338 (1967).

Hoffman, R. C.

Kato, S.

T. Ohno, S. Kato, A. Yamada, T. Tanno, J. Phys. Chem. 87, 775 (1983).
[CrossRef]

Kelly, J. M.

W. Blau, H. Byrne, W. M. Dennis, J. M. Kelly, Opt. Commun. 56, 25 (1985).
[CrossRef]

Kenney, M. E.

P. A. Firey, W. E. Ford, J. R. Sounik, M. E. Kenney, M. A. Rodgers, J. Am. Chem. Soc. 110, 7626 (1988).
[CrossRef]

J. N. Esposito, L. E. Sutton, M. E. Kenney, Inorg. Chem. 6, 1116 (1967).
[CrossRef]

Kost, A.

L. W. Tutt, A. Kost, Nature (London) 356, 225 (1992).
[CrossRef]

Magde, D.

J. H. Brannon, D. Magde, J. Am. Chem. Soc. 102, 62 (1980).
[CrossRef]

McCahon, S. W.

McLean, D. G.

Miles, P. A.

P. A. Miles, “‘Bottleneck’ optical limiters—the optimal use of excited-state absorbers,” Appl. Opt. (to be published).

Miskowski, V. M.

D. R. Coulter, V. M. Miskowski, J. W. Perry, T. H. Wie, E. W. Van Stryland, D. J. Hagan, Proc. Soc. Photo-Opt. Instrum. Eng. 1105, 42 (1989).

Ohno, T.

T. Ohno, S. Kato, A. Yamada, T. Tanno, J. Phys. Chem. 87, 775 (1983).
[CrossRef]

Perry, J. W.

T. H. Wie, D. J. Hagan, M. J. Sence, E. W. Van Stryland, J. W. Perry, D. R. Coulter, Appl. Phys. B 54, 46 (1992).
[CrossRef]

D. R. Coulter, V. M. Miskowski, J. W. Perry, T. H. Wie, E. W. Van Stryland, D. J. Hagan, Proc. Soc. Photo-Opt. Instrum. Eng. 1105, 42 (1989).

Pong, R. G. S.

J. S. Shirk, R. G. S. Pong, F. J. Bartoli, A. W. Snow, Appl. Phys. Lett 63, 1880 (1993).
[CrossRef]

Potember, R. S.

Rodgers, M. A.

P. A. Firey, W. E. Ford, J. R. Sounik, M. E. Kenney, M. A. Rodgers, J. Am. Chem. Soc. 110, 7626 (1988).
[CrossRef]

Rubin, Y.

J. W. Arbogast, A. P. Darmanyan, C. S. Foote, Y. Rubin, F. N. Diederich, M. Alvarez, S. J. Anz, R. L. Whetten, J. Phys. Chem. 1991, 11 (1991).
[CrossRef]

Sence, M. J.

T. H. Wie, D. J. Hagan, M. J. Sence, E. W. Van Stryland, J. W. Perry, D. R. Coulter, Appl. Phys. B 54, 46 (1992).
[CrossRef]

Shirk, J. S.

J. S. Shirk, R. G. S. Pong, F. J. Bartoli, A. W. Snow, Appl. Phys. Lett 63, 1880 (1993).
[CrossRef]

Snow, A. W.

J. S. Shirk, R. G. S. Pong, F. J. Bartoli, A. W. Snow, Appl. Phys. Lett 63, 1880 (1993).
[CrossRef]

Sounik, J. R.

P. A. Firey, W. E. Ford, J. R. Sounik, M. E. Kenney, M. A. Rodgers, J. Am. Chem. Soc. 110, 7626 (1988).
[CrossRef]

Stetyick, K. A.

Sutton, L. E.

J. N. Esposito, L. E. Sutton, M. E. Kenney, Inorg. Chem. 6, 1116 (1967).
[CrossRef]

Tanno, T.

T. Ohno, S. Kato, A. Yamada, T. Tanno, J. Phys. Chem. 87, 775 (1983).
[CrossRef]

Tutt, L. W.

L. W. Tutt, A. Kost, Nature (London) 356, 225 (1992).
[CrossRef]

L. W. Tutt, S. W. McCahon, Opt. Lett. 15, 700 (1990).
[CrossRef] [PubMed]

Van Stryland, E. W.

T. H. Wie, D. J. Hagan, M. J. Sence, E. W. Van Stryland, J. W. Perry, D. R. Coulter, Appl. Phys. B 54, 46 (1992).
[CrossRef]

D. R. Coulter, V. M. Miskowski, J. W. Perry, T. H. Wie, E. W. Van Stryland, D. J. Hagan, Proc. Soc. Photo-Opt. Instrum. Eng. 1105, 42 (1989).

Whetten, R. L.

J. W. Arbogast, A. P. Darmanyan, C. S. Foote, Y. Rubin, F. N. Diederich, M. Alvarez, S. J. Anz, R. L. Whetten, J. Phys. Chem. 1991, 11 (1991).
[CrossRef]

Wie, T. H.

T. H. Wie, D. J. Hagan, M. J. Sence, E. W. Van Stryland, J. W. Perry, D. R. Coulter, Appl. Phys. B 54, 46 (1992).
[CrossRef]

D. R. Coulter, V. M. Miskowski, J. W. Perry, T. H. Wie, E. W. Van Stryland, D. J. Hagan, Proc. Soc. Photo-Opt. Instrum. Eng. 1105, 42 (1989).

Yamada, A.

T. Ohno, S. Kato, A. Yamada, T. Tanno, J. Phys. Chem. 87, 775 (1983).
[CrossRef]

Appl. Phys. B

T. H. Wie, D. J. Hagan, M. J. Sence, E. W. Van Stryland, J. W. Perry, D. R. Coulter, Appl. Phys. B 54, 46 (1992).
[CrossRef]

Appl. Phys. Lett

J. S. Shirk, R. G. S. Pong, F. J. Bartoli, A. W. Snow, Appl. Phys. Lett 63, 1880 (1993).
[CrossRef]

IEEE J. Quantum Electron.

C. R. Guiliano, L. D. Hess, IEEE J. Quantum Electron. QE-3, 338 (1967).

Inorg. Chem.

J. N. Esposito, L. E. Sutton, M. E. Kenney, Inorg. Chem. 6, 1116 (1967).
[CrossRef]

J. Am. Chem. Soc.

P. A. Firey, W. E. Ford, J. R. Sounik, M. E. Kenney, M. A. Rodgers, J. Am. Chem. Soc. 110, 7626 (1988).
[CrossRef]

J. H. Brannon, D. Magde, J. Am. Chem. Soc. 102, 62 (1980).
[CrossRef]

J. Opt. Soc. Am. B

J. Phys. Chem.

T. Ohno, S. Kato, A. Yamada, T. Tanno, J. Phys. Chem. 87, 775 (1983).
[CrossRef]

J. W. Arbogast, A. P. Darmanyan, C. S. Foote, Y. Rubin, F. N. Diederich, M. Alvarez, S. J. Anz, R. L. Whetten, J. Phys. Chem. 1991, 11 (1991).
[CrossRef]

Nature

L. W. Tutt, A. Kost, Nature (London) 356, 225 (1992).
[CrossRef]

Opt. Commun.

W. Blau, H. Byrne, W. M. Dennis, J. M. Kelly, Opt. Commun. 56, 25 (1985).
[CrossRef]

Opt. Lett.

Proc. Soc. Photo-Opt. Instrum. Eng.

D. R. Coulter, V. M. Miskowski, J. W. Perry, T. H. Wie, E. W. Van Stryland, D. J. Hagan, Proc. Soc. Photo-Opt. Instrum. Eng. 1105, 42 (1989).

Other

P. A. Miles, “‘Bottleneck’ optical limiters—the optimal use of excited-state absorbers,” Appl. Opt. (to be published).

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Figures (3)

Fig. 1
Fig. 1

Electronic absorption spectrum of bis[tri-(n-hexyl)siloxy]SnPc in toluene solution at 7.1 × 10−6 M. Also shown (curve with circles) is the transient absorption spectrum (arbitrary units) of Sn Pc in toluene obtained 100 ns after excitation at 355 nm.

Fig. 2
Fig. 2

Nonlinear transmittance of group IIIA (upper curves: Al, open circles; Ga, open triangles; In, filled squares) and group IVA (lower curves: Si, plus sign; Ge, open squares; Sn, filled circles) metal-substituted Pc’s in toluene solution measured with 8-ns, 532-nm laser pulses and an f/40 optical geometry. Solutions had 84% linear transmission at 532 nm for a 1-cm path length, which corresponds to a concentration of ~ 1.4 × 10−4 M. The upper curves have been displaced vertically by 0.4 for presentation.

Fig. 3
Fig. 3

The f/8 optical-limiting response of Pb Pc and SiNc in toluene and of CAP in methanol at 532 nm. The input lens had a 2.5-cm diameter and 4-cm focal length; the laser beam diameter was 4.8 mm (full width at 1/e2 maximum intensity) at the lens; the calculated beam waist was 10 μm (half-width at 1/e2 maximum intensity); and the focus was close to the exit window of the 1-cm cell. The transmitted energy was collected at ~f/2 and relayed to a 1.5-mm spot size on a 1-cm-diameter detector. Solutions had a linear transmittance of 0.3 at 532 nm; concentrations were 7 × 10−4 M for SiNc, 9 × 10−4 M for CAP, and 1.3 × 10−3 M for Pb Pc.

Tables (1)

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Table 1 Photophysical Properties for Group IIIA and Group IVA Metal Pc’s

Equations (1)

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σ eff / σ g = ln T sat / ln T lin ( σ s f s + σ t f t ) / σ g ,

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