Abstract

A new instrument for the measurement of short fluorescence lifetimes is discussed and characterized. The instrument is basically an implementation of the cross-correlation between the excitation source and the induced fluorescence response. Such an approach, with a mode-locked argon-ion laser as the source, is shown to be capable of measuring lifetimes as short as 80 psec with a precision of 10 psec.

© 1979 Optical Society of America

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References

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  1. W. R. Ware, in Creation and Detection of the Excited State, A. A. Lamola, Ed. (Marcel Dekker, New York, 1971), Vol. 1A, p. 213.
  2. I. Isenberg, in Biochemical Fluorescence Concepts, R. F. Chen, H. Edelhoch, Eds. (Marcel Dekker, New York, 1975), Vol. 1, p. 43.
  3. M. R. Loken, J. R. Gohlke, L. Brand, in Fluorescence Techniques in Cell Biology, A. A. Thaer, M. Sernetz, Eds. (Springer, New York, 1973), p. 339.
    [CrossRef]
  4. D. M. Rayner, A. G. Szabo, Appl. Opt. 17, 1624 (1978).
    [CrossRef] [PubMed]
  5. B. Leskovar, C. C. Lo, P. R. Hartig, K. Sauer, Rev. Sci. Instrum. 47, 1113 (1976).
    [CrossRef]
  6. P. R. Hartig, K. Sauer, C. C. Lo, B. Leskovar, Rev. Sci. Instrum. 47, 1122 (1976).
    [CrossRef] [PubMed]
  7. R. Spencer, G. Weber, Ann. N.Y. Acad. Sci. 158, 361 (1969).
    [CrossRef]
  8. E. R. Menzel, Z. D. Popovic, Rev. Sci. Instrum. 49, 39 (1978).
    [CrossRef] [PubMed]
  9. G. Mourou, M. M. Malley, Opt. Commun. 11, 282 (1974).
    [CrossRef]
  10. G. R. Haugen, B. W. Wallin, F. E. Lytle, Rev. Sci. Instrum. 50, 64 (1979).
    [CrossRef] [PubMed]
  11. J. S. Bendat, A. G. Piersol, Random Data: Analysis and Measurement Procedures (Wiley-Interscience, New York, 1971).
  12. N. S. Nahman, Proc. IEEE 66, 441 (1978).
    [CrossRef]
  13. This is another way of writing the correlation function for non-square integrable functions. Normally it is written Cij(τ)=limT→∞12T∫-T+Ti(t)j(t+τ)dt, where both i and j are nonsquare integrable, such as periodic, functions.
  14. Z. Kam, H. B. Shore, G. Feher, Rev. Sci. Instrum. 46, 269 (1975).
    [CrossRef]
  15. L. Steinmetz, Rev. Sci. Instrum. (in press, 1979).
  16. R. H. Wilcox, Rev. Sci. Instrum. 30, 1009 (1959).
    [CrossRef]
  17. H. E. Zimmerman, D. P. Werthemann, K. S. Kamm, J. Am. Chem. Soc. 96, 439 (1974).
    [CrossRef]
  18. B. Sipp, J. A. Miehe, R. Lopez-Delgado, Opt. Commun. 16, 202 (1976).
    [CrossRef]
  19. Ph. Wahl, J. C. Auchet, B. Donzel, Rev. Sci. Instrum. 45, 28 (1974).
    [CrossRef]
  20. L. A. Shaver, L. J. Cline-Love, Appl. Spectrosc. 29, 485 (1975).
    [CrossRef]
  21. J. M. Harris, F. E. Lytle, Rev. Sci. Instrum. 48, 1469 (1977).
    [CrossRef]
  22. I. B. Berlman, Handbook of Fluorescence Spectra of Aromatic Molecules (Academic, New York, 1971).
  23. G. M. Hieftje, G. R. Haugen, J. M. Ramsey, Appl. Phys. Lett. 30, 463 (1977).
    [CrossRef]
  24. R. R. Alfano, S. L. Shapiro, Opt. Commun. 6, 98 (1972).
    [CrossRef]
  25. L. A. Shaver, L. J. Cline-Love, in Progress in Analytical Chemistry, I. L. Simmons, G. W. Ewing, Eds. (Plenum, New York, 1975), Vol. 8, p. 249.
  26. H. D. Young, Statistical Treatment of Experimental Data (McGraw-Hill, New York, 1962).

1979 (1)

G. R. Haugen, B. W. Wallin, F. E. Lytle, Rev. Sci. Instrum. 50, 64 (1979).
[CrossRef] [PubMed]

1978 (3)

N. S. Nahman, Proc. IEEE 66, 441 (1978).
[CrossRef]

E. R. Menzel, Z. D. Popovic, Rev. Sci. Instrum. 49, 39 (1978).
[CrossRef] [PubMed]

D. M. Rayner, A. G. Szabo, Appl. Opt. 17, 1624 (1978).
[CrossRef] [PubMed]

1977 (2)

J. M. Harris, F. E. Lytle, Rev. Sci. Instrum. 48, 1469 (1977).
[CrossRef]

G. M. Hieftje, G. R. Haugen, J. M. Ramsey, Appl. Phys. Lett. 30, 463 (1977).
[CrossRef]

1976 (3)

B. Sipp, J. A. Miehe, R. Lopez-Delgado, Opt. Commun. 16, 202 (1976).
[CrossRef]

B. Leskovar, C. C. Lo, P. R. Hartig, K. Sauer, Rev. Sci. Instrum. 47, 1113 (1976).
[CrossRef]

P. R. Hartig, K. Sauer, C. C. Lo, B. Leskovar, Rev. Sci. Instrum. 47, 1122 (1976).
[CrossRef] [PubMed]

1975 (2)

Z. Kam, H. B. Shore, G. Feher, Rev. Sci. Instrum. 46, 269 (1975).
[CrossRef]

L. A. Shaver, L. J. Cline-Love, Appl. Spectrosc. 29, 485 (1975).
[CrossRef]

1974 (3)

H. E. Zimmerman, D. P. Werthemann, K. S. Kamm, J. Am. Chem. Soc. 96, 439 (1974).
[CrossRef]

Ph. Wahl, J. C. Auchet, B. Donzel, Rev. Sci. Instrum. 45, 28 (1974).
[CrossRef]

G. Mourou, M. M. Malley, Opt. Commun. 11, 282 (1974).
[CrossRef]

1972 (1)

R. R. Alfano, S. L. Shapiro, Opt. Commun. 6, 98 (1972).
[CrossRef]

1969 (1)

R. Spencer, G. Weber, Ann. N.Y. Acad. Sci. 158, 361 (1969).
[CrossRef]

1959 (1)

R. H. Wilcox, Rev. Sci. Instrum. 30, 1009 (1959).
[CrossRef]

Alfano, R. R.

R. R. Alfano, S. L. Shapiro, Opt. Commun. 6, 98 (1972).
[CrossRef]

Auchet, J. C.

Ph. Wahl, J. C. Auchet, B. Donzel, Rev. Sci. Instrum. 45, 28 (1974).
[CrossRef]

Bendat, J. S.

J. S. Bendat, A. G. Piersol, Random Data: Analysis and Measurement Procedures (Wiley-Interscience, New York, 1971).

Berlman, I. B.

I. B. Berlman, Handbook of Fluorescence Spectra of Aromatic Molecules (Academic, New York, 1971).

Brand, L.

M. R. Loken, J. R. Gohlke, L. Brand, in Fluorescence Techniques in Cell Biology, A. A. Thaer, M. Sernetz, Eds. (Springer, New York, 1973), p. 339.
[CrossRef]

Cline-Love, L. J.

L. A. Shaver, L. J. Cline-Love, Appl. Spectrosc. 29, 485 (1975).
[CrossRef]

L. A. Shaver, L. J. Cline-Love, in Progress in Analytical Chemistry, I. L. Simmons, G. W. Ewing, Eds. (Plenum, New York, 1975), Vol. 8, p. 249.

Donzel, B.

Ph. Wahl, J. C. Auchet, B. Donzel, Rev. Sci. Instrum. 45, 28 (1974).
[CrossRef]

Feher, G.

Z. Kam, H. B. Shore, G. Feher, Rev. Sci. Instrum. 46, 269 (1975).
[CrossRef]

Gohlke, J. R.

M. R. Loken, J. R. Gohlke, L. Brand, in Fluorescence Techniques in Cell Biology, A. A. Thaer, M. Sernetz, Eds. (Springer, New York, 1973), p. 339.
[CrossRef]

Harris, J. M.

J. M. Harris, F. E. Lytle, Rev. Sci. Instrum. 48, 1469 (1977).
[CrossRef]

Hartig, P. R.

B. Leskovar, C. C. Lo, P. R. Hartig, K. Sauer, Rev. Sci. Instrum. 47, 1113 (1976).
[CrossRef]

P. R. Hartig, K. Sauer, C. C. Lo, B. Leskovar, Rev. Sci. Instrum. 47, 1122 (1976).
[CrossRef] [PubMed]

Haugen, G. R.

G. R. Haugen, B. W. Wallin, F. E. Lytle, Rev. Sci. Instrum. 50, 64 (1979).
[CrossRef] [PubMed]

G. M. Hieftje, G. R. Haugen, J. M. Ramsey, Appl. Phys. Lett. 30, 463 (1977).
[CrossRef]

Hieftje, G. M.

G. M. Hieftje, G. R. Haugen, J. M. Ramsey, Appl. Phys. Lett. 30, 463 (1977).
[CrossRef]

Isenberg, I.

I. Isenberg, in Biochemical Fluorescence Concepts, R. F. Chen, H. Edelhoch, Eds. (Marcel Dekker, New York, 1975), Vol. 1, p. 43.

Kam, Z.

Z. Kam, H. B. Shore, G. Feher, Rev. Sci. Instrum. 46, 269 (1975).
[CrossRef]

Kamm, K. S.

H. E. Zimmerman, D. P. Werthemann, K. S. Kamm, J. Am. Chem. Soc. 96, 439 (1974).
[CrossRef]

Leskovar, B.

B. Leskovar, C. C. Lo, P. R. Hartig, K. Sauer, Rev. Sci. Instrum. 47, 1113 (1976).
[CrossRef]

P. R. Hartig, K. Sauer, C. C. Lo, B. Leskovar, Rev. Sci. Instrum. 47, 1122 (1976).
[CrossRef] [PubMed]

Lo, C. C.

B. Leskovar, C. C. Lo, P. R. Hartig, K. Sauer, Rev. Sci. Instrum. 47, 1113 (1976).
[CrossRef]

P. R. Hartig, K. Sauer, C. C. Lo, B. Leskovar, Rev. Sci. Instrum. 47, 1122 (1976).
[CrossRef] [PubMed]

Loken, M. R.

M. R. Loken, J. R. Gohlke, L. Brand, in Fluorescence Techniques in Cell Biology, A. A. Thaer, M. Sernetz, Eds. (Springer, New York, 1973), p. 339.
[CrossRef]

Lopez-Delgado, R.

B. Sipp, J. A. Miehe, R. Lopez-Delgado, Opt. Commun. 16, 202 (1976).
[CrossRef]

Lytle, F. E.

G. R. Haugen, B. W. Wallin, F. E. Lytle, Rev. Sci. Instrum. 50, 64 (1979).
[CrossRef] [PubMed]

J. M. Harris, F. E. Lytle, Rev. Sci. Instrum. 48, 1469 (1977).
[CrossRef]

Malley, M. M.

G. Mourou, M. M. Malley, Opt. Commun. 11, 282 (1974).
[CrossRef]

Menzel, E. R.

E. R. Menzel, Z. D. Popovic, Rev. Sci. Instrum. 49, 39 (1978).
[CrossRef] [PubMed]

Miehe, J. A.

B. Sipp, J. A. Miehe, R. Lopez-Delgado, Opt. Commun. 16, 202 (1976).
[CrossRef]

Mourou, G.

G. Mourou, M. M. Malley, Opt. Commun. 11, 282 (1974).
[CrossRef]

Nahman, N. S.

N. S. Nahman, Proc. IEEE 66, 441 (1978).
[CrossRef]

Piersol, A. G.

J. S. Bendat, A. G. Piersol, Random Data: Analysis and Measurement Procedures (Wiley-Interscience, New York, 1971).

Popovic, Z. D.

E. R. Menzel, Z. D. Popovic, Rev. Sci. Instrum. 49, 39 (1978).
[CrossRef] [PubMed]

Ramsey, J. M.

G. M. Hieftje, G. R. Haugen, J. M. Ramsey, Appl. Phys. Lett. 30, 463 (1977).
[CrossRef]

Rayner, D. M.

Sauer, K.

P. R. Hartig, K. Sauer, C. C. Lo, B. Leskovar, Rev. Sci. Instrum. 47, 1122 (1976).
[CrossRef] [PubMed]

B. Leskovar, C. C. Lo, P. R. Hartig, K. Sauer, Rev. Sci. Instrum. 47, 1113 (1976).
[CrossRef]

Shapiro, S. L.

R. R. Alfano, S. L. Shapiro, Opt. Commun. 6, 98 (1972).
[CrossRef]

Shaver, L. A.

L. A. Shaver, L. J. Cline-Love, Appl. Spectrosc. 29, 485 (1975).
[CrossRef]

L. A. Shaver, L. J. Cline-Love, in Progress in Analytical Chemistry, I. L. Simmons, G. W. Ewing, Eds. (Plenum, New York, 1975), Vol. 8, p. 249.

Shore, H. B.

Z. Kam, H. B. Shore, G. Feher, Rev. Sci. Instrum. 46, 269 (1975).
[CrossRef]

Sipp, B.

B. Sipp, J. A. Miehe, R. Lopez-Delgado, Opt. Commun. 16, 202 (1976).
[CrossRef]

Spencer, R.

R. Spencer, G. Weber, Ann. N.Y. Acad. Sci. 158, 361 (1969).
[CrossRef]

Steinmetz, L.

L. Steinmetz, Rev. Sci. Instrum. (in press, 1979).

Szabo, A. G.

Wahl, Ph.

Ph. Wahl, J. C. Auchet, B. Donzel, Rev. Sci. Instrum. 45, 28 (1974).
[CrossRef]

Wallin, B. W.

G. R. Haugen, B. W. Wallin, F. E. Lytle, Rev. Sci. Instrum. 50, 64 (1979).
[CrossRef] [PubMed]

Ware, W. R.

W. R. Ware, in Creation and Detection of the Excited State, A. A. Lamola, Ed. (Marcel Dekker, New York, 1971), Vol. 1A, p. 213.

Weber, G.

R. Spencer, G. Weber, Ann. N.Y. Acad. Sci. 158, 361 (1969).
[CrossRef]

Werthemann, D. P.

H. E. Zimmerman, D. P. Werthemann, K. S. Kamm, J. Am. Chem. Soc. 96, 439 (1974).
[CrossRef]

Wilcox, R. H.

R. H. Wilcox, Rev. Sci. Instrum. 30, 1009 (1959).
[CrossRef]

Young, H. D.

H. D. Young, Statistical Treatment of Experimental Data (McGraw-Hill, New York, 1962).

Zimmerman, H. E.

H. E. Zimmerman, D. P. Werthemann, K. S. Kamm, J. Am. Chem. Soc. 96, 439 (1974).
[CrossRef]

Ann. N.Y. Acad. Sci. (1)

R. Spencer, G. Weber, Ann. N.Y. Acad. Sci. 158, 361 (1969).
[CrossRef]

Appl. Opt. (1)

Appl. Phys. Lett. (1)

G. M. Hieftje, G. R. Haugen, J. M. Ramsey, Appl. Phys. Lett. 30, 463 (1977).
[CrossRef]

Appl. Spectrosc. (1)

J. Am. Chem. Soc. (1)

H. E. Zimmerman, D. P. Werthemann, K. S. Kamm, J. Am. Chem. Soc. 96, 439 (1974).
[CrossRef]

Opt. Commun. (3)

B. Sipp, J. A. Miehe, R. Lopez-Delgado, Opt. Commun. 16, 202 (1976).
[CrossRef]

G. Mourou, M. M. Malley, Opt. Commun. 11, 282 (1974).
[CrossRef]

R. R. Alfano, S. L. Shapiro, Opt. Commun. 6, 98 (1972).
[CrossRef]

Proc. IEEE (1)

N. S. Nahman, Proc. IEEE 66, 441 (1978).
[CrossRef]

Rev. Sci. Instrum. (8)

G. R. Haugen, B. W. Wallin, F. E. Lytle, Rev. Sci. Instrum. 50, 64 (1979).
[CrossRef] [PubMed]

E. R. Menzel, Z. D. Popovic, Rev. Sci. Instrum. 49, 39 (1978).
[CrossRef] [PubMed]

B. Leskovar, C. C. Lo, P. R. Hartig, K. Sauer, Rev. Sci. Instrum. 47, 1113 (1976).
[CrossRef]

P. R. Hartig, K. Sauer, C. C. Lo, B. Leskovar, Rev. Sci. Instrum. 47, 1122 (1976).
[CrossRef] [PubMed]

Ph. Wahl, J. C. Auchet, B. Donzel, Rev. Sci. Instrum. 45, 28 (1974).
[CrossRef]

Z. Kam, H. B. Shore, G. Feher, Rev. Sci. Instrum. 46, 269 (1975).
[CrossRef]

J. M. Harris, F. E. Lytle, Rev. Sci. Instrum. 48, 1469 (1977).
[CrossRef]

R. H. Wilcox, Rev. Sci. Instrum. 30, 1009 (1959).
[CrossRef]

Other (9)

L. A. Shaver, L. J. Cline-Love, in Progress in Analytical Chemistry, I. L. Simmons, G. W. Ewing, Eds. (Plenum, New York, 1975), Vol. 8, p. 249.

H. D. Young, Statistical Treatment of Experimental Data (McGraw-Hill, New York, 1962).

I. B. Berlman, Handbook of Fluorescence Spectra of Aromatic Molecules (Academic, New York, 1971).

L. Steinmetz, Rev. Sci. Instrum. (in press, 1979).

W. R. Ware, in Creation and Detection of the Excited State, A. A. Lamola, Ed. (Marcel Dekker, New York, 1971), Vol. 1A, p. 213.

I. Isenberg, in Biochemical Fluorescence Concepts, R. F. Chen, H. Edelhoch, Eds. (Marcel Dekker, New York, 1975), Vol. 1, p. 43.

M. R. Loken, J. R. Gohlke, L. Brand, in Fluorescence Techniques in Cell Biology, A. A. Thaer, M. Sernetz, Eds. (Springer, New York, 1973), p. 339.
[CrossRef]

J. S. Bendat, A. G. Piersol, Random Data: Analysis and Measurement Procedures (Wiley-Interscience, New York, 1971).

This is another way of writing the correlation function for non-square integrable functions. Normally it is written Cij(τ)=limT→∞12T∫-T+Ti(t)j(t+τ)dt, where both i and j are nonsquare integrable, such as periodic, functions.

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Figures (4)

Fig. 1
Fig. 1

Schematic diagram of cross-correlation instrument. BS1 and BS2, beam splitters; ND1 and ND2, neutral density filters; PD1 and PD2, photodiodes; M1, M2, M3 and M4, dielectric-coated mirrors; VND, variable neutral density filter; CC1 and CC2, corner cubes; C, fluorescence sample cell; BD, beam stop; IF, interference filter; PMT, photomultiplier tube; LS, microwave line stretcher; PS, microwave power splitter; MULT, microwave mixer; L1, L2, L3, lenses; term, 50-Ω microwave load.

Fig. 2
Fig. 2

Time-dependent output of Schottky photodiode when illuminated with mode-locked argon-ion laser. Measured with sampling oscilloscope, τr = 75 psec.

Fig. 3
Fig. 3

Comparison of new correlator with sampling oscilloscope measurement: (A) output of cross-correlation instrument for detection of a laser pulse; (B) sampling oscilloscope display of laser pulse.

Fig. 4
Fig. 4

Fluorescence decay curves obtained with new correlation lifetime fluorimeter: (A) rhodamine B lifetime determination (1 × 10−6 M in EtOH, τ = 2.77 nsec). Earliest broken peak is instrument response function. Later broken peak is experimental fluorescence decay curve. Solid curve is calculated decay curve. (B) Same as (A) but for disodium fluorescein (2.42 × 10−5 M in H2O with 0.01-M NaOH and 0.8-M KI, τ = 0.36 nsec).

Tables (1)

Tables Icon

Table I Fluorescence Lifetime Results

Equations (16)

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D ( t ) = - h d ( γ ) l ( t - γ ) d γ ,
P ( t ) = - h p ( ζ ) l ( t - ζ ) d ζ ,
I ( τ ) = A - D ( t ) P ( t + τ ) d t .
I ( τ ) = A - h d ( γ ) h p ( ζ ) l ( t - γ ) l ( t + τ - ζ ) d ζ d γ d t .
I ( τ ) = A - h d ( γ ) h p ( ζ ) C l l ( τ + γ - ζ ) d ζ d γ ,
P ( t ) = - F ( ν ) P ( t - ν ) d ν ,
I ( τ ) = A - h d ( γ ) h p ( ζ ) F ( ν ) l ( t - γ ) l ( t + τ - ν - ζ ) d t d ν d ζ d γ .
I ( τ ) = A - h d ( γ ) h p ( ζ ) F ( ν ) C l l ( τ + γ - ν - ζ ) d ν d ζ d γ .
I ( τ ) = - F ( ν ) I ( τ - ν ) d ν .
l e ( t ) = n = - l ( t - n T ) ,
I e ( τ ) = lim M A 2 M T - M T + M T - + n = - i = - h d ( γ ) h p ( ζ ) l ( t - γ - n T ) l ( t + τ - ζ - i T ) d ζ d γ d t .
lim M 1 2 M T
I e ( τ ) = A T k = - - h d ( γ ) h p ( ζ ) C l l ( τ - ζ + γ + k T ) d γ d ζ ,
lim T 1 2 T - T T f ( t ) d t .
σ τ = ( d 2 M d τ 2 ) 1 / 2 .
Cij(τ)=limT12T-T+Ti(t)j(t+τ)dt,

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