Abstract

Improved nonlinear organic chromophores of varying conjugation length with either thiobarbituric acid or 3-dicyanomethylene-2,3-dihydrobenzothiophene-1,1-dioxide (FORON® Blue) acceptors have been synthesized and investigated for their nonlinear optical properties. Very large quadratic hyperpolarizabilities β(-2ω;ω,ω) have been found, up to 25,700×10-48 esu at λ=1.91 µm. In a guest–host polymer very high electro-optic (EO) coefficients, of up to 55 pm/V, have been determined at λ=1.31 µm with 20-wt % chromophore loading. We find good agreement between molecular parameters evaluated by electric-field-induced second-harmonic generation (EFISH) and the measurements of guest–host solid–solid solutions. The latter method is well suited to the determination of the product of dipole moment μ and hyperpolarizability β quickly and reliably at the wavelength of interest for EO applications without the complications associated with EFISH measurements.

© 1996 Optical Society of America

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  1. S. R. Marder, L.-T. Cheng, B. G. Tiemann, A. C. Friedli, M. Blanchard-Desce, J. W. Perry, and J. Skindhøj, Science 263, 511(1994).
    [CrossRef] [PubMed]
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    [CrossRef]
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    [CrossRef]
  4. M. Ahlheim, M. Barzoukas, P. V. Bedworth, M. Blanchard-Desce, A. Fort, Z.-Y. Hu, S. R. Marder, J. W. Perry, C. Runser, M. Stähelin, and B. Zysset, Science 271, 335(1996).
    [CrossRef]
  5. FORON® Blue is a registered trademark of SANDOZ Ltd., Basel, Switzerland.
  6. British Patent GB 2026528 (1980); French Patent Fr 2438045 (1980). Both are held by Sandoz Ltd. (inventor, W. Baumann).
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    [CrossRef]
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    [CrossRef]
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    [CrossRef]
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    [CrossRef]
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    [CrossRef]
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    [CrossRef]
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    [CrossRef]
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    [CrossRef]
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    [CrossRef]
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    [CrossRef]
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    [CrossRef]
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    [CrossRef]
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    [CrossRef]
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    [CrossRef]
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    [CrossRef]
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    [CrossRef]

1996

M. Ahlheim, M. Barzoukas, P. V. Bedworth, M. Blanchard-Desce, A. Fort, Z.-Y. Hu, S. R. Marder, J. W. Perry, C. Runser, M. Stähelin, and B. Zysset, Science 271, 335(1996).
[CrossRef]

1994

S. R. Marder, L.-T. Cheng, B. G. Tiemann, A. C. Friedli, M. Blanchard-Desce, J. W. Perry, and J. Skindhøj, Science 263, 511(1994).
[CrossRef] [PubMed]

P. Prêtre, P. Kaatz, A. Bohren, P. Günter, B. Zysset, M. Ahlheim, M. Stähelin, and F. Lehr, Macromolecules 27, 5476(1994).
[CrossRef]

1993

C. R. Moylan, R. J. Twieg, V. Y. Lee, S. A. Swanson, K. M. Betterton, and R. D. Miller, J. Am. Chem. Soc. 115, 12599(1993).
[CrossRef]

V. P. Rao, A. K-Y. Jen, K. Y. Wong, and K. J. Drost, J. Chem. Soc. Chem. Commun. 1118–1120(1993).
[CrossRef]

1992

A. Willetts, J. E. Rice, D. M. Burland, and D. P. Shelton, J. Chem. Phys. 97, 7590(1992).
[CrossRef]

1990

C. C. Teng and H. T. Man, Appl. Phys. Lett. 56, 1734(1990).
[CrossRef]

1987

1982

I. Ledoux and J. Zyss, Chem. Phys. 73, 203(1982).
[CrossRef]

1977

J.-L. Oudar, J. Chem. Phys. 67, 446(1977).
[CrossRef]

1975

B. F. Levine and C. G. Bethea, J. Chem. Phys. 63, 2666(1975).
[CrossRef]

1974

B. Levine and C. Bethea, Appl. Phys. Lett. 24, 445(1974).
[CrossRef]

Ahlheim, M.

M. Ahlheim, M. Barzoukas, P. V. Bedworth, M. Blanchard-Desce, A. Fort, Z.-Y. Hu, S. R. Marder, J. W. Perry, C. Runser, M. Stähelin, and B. Zysset, Science 271, 335(1996).
[CrossRef]

P. Prêtre, P. Kaatz, A. Bohren, P. Günter, B. Zysset, M. Ahlheim, M. Stähelin, and F. Lehr, Macromolecules 27, 5476(1994).
[CrossRef]

Barzoukas, M.

M. Ahlheim, M. Barzoukas, P. V. Bedworth, M. Blanchard-Desce, A. Fort, Z.-Y. Hu, S. R. Marder, J. W. Perry, C. Runser, M. Stähelin, and B. Zysset, Science 271, 335(1996).
[CrossRef]

Bedworth, P. V.

M. Ahlheim, M. Barzoukas, P. V. Bedworth, M. Blanchard-Desce, A. Fort, Z.-Y. Hu, S. R. Marder, J. W. Perry, C. Runser, M. Stähelin, and B. Zysset, Science 271, 335(1996).
[CrossRef]

Bethea, C.

B. Levine and C. Bethea, Appl. Phys. Lett. 24, 445(1974).
[CrossRef]

Bethea, C. G.

B. F. Levine and C. G. Bethea, J. Chem. Phys. 63, 2666(1975).
[CrossRef]

Betterton, K. M.

C. R. Moylan, R. J. Twieg, V. Y. Lee, S. A. Swanson, K. M. Betterton, and R. D. Miller, J. Am. Chem. Soc. 115, 12599(1993).
[CrossRef]

Blanchard-Desce, M.

M. Ahlheim, M. Barzoukas, P. V. Bedworth, M. Blanchard-Desce, A. Fort, Z.-Y. Hu, S. R. Marder, J. W. Perry, C. Runser, M. Stähelin, and B. Zysset, Science 271, 335(1996).
[CrossRef]

S. R. Marder, L.-T. Cheng, B. G. Tiemann, A. C. Friedli, M. Blanchard-Desce, J. W. Perry, and J. Skindhøj, Science 263, 511(1994).
[CrossRef] [PubMed]

Bohren, A.

P. Prêtre, P. Kaatz, A. Bohren, P. Günter, B. Zysset, M. Ahlheim, M. Stähelin, and F. Lehr, Macromolecules 27, 5476(1994).
[CrossRef]

Burland, D. M.

A. Willetts, J. E. Rice, D. M. Burland, and D. P. Shelton, J. Chem. Phys. 97, 7590(1992).
[CrossRef]

Cheng, L.-T.

S. R. Marder, L.-T. Cheng, B. G. Tiemann, A. C. Friedli, M. Blanchard-Desce, J. W. Perry, and J. Skindhøj, Science 263, 511(1994).
[CrossRef] [PubMed]

Drost, K. J.

V. P. Rao, A. K-Y. Jen, K. Y. Wong, and K. J. Drost, J. Chem. Soc. Chem. Commun. 1118–1120(1993).
[CrossRef]

Fort, A.

M. Ahlheim, M. Barzoukas, P. V. Bedworth, M. Blanchard-Desce, A. Fort, Z.-Y. Hu, S. R. Marder, J. W. Perry, C. Runser, M. Stähelin, and B. Zysset, Science 271, 335(1996).
[CrossRef]

Friedli, A. C.

S. R. Marder, L.-T. Cheng, B. G. Tiemann, A. C. Friedli, M. Blanchard-Desce, J. W. Perry, and J. Skindhøj, Science 263, 511(1994).
[CrossRef] [PubMed]

Günter, P.

P. Prêtre, P. Kaatz, A. Bohren, P. Günter, B. Zysset, M. Ahlheim, M. Stähelin, and F. Lehr, Macromolecules 27, 5476(1994).
[CrossRef]

Hu, Z.-Y.

M. Ahlheim, M. Barzoukas, P. V. Bedworth, M. Blanchard-Desce, A. Fort, Z.-Y. Hu, S. R. Marder, J. W. Perry, C. Runser, M. Stähelin, and B. Zysset, Science 271, 335(1996).
[CrossRef]

Jen, A. K-Y.

V. P. Rao, A. K-Y. Jen, K. Y. Wong, and K. J. Drost, J. Chem. Soc. Chem. Commun. 1118–1120(1993).
[CrossRef]

Kaatz, P.

P. Prêtre, P. Kaatz, A. Bohren, P. Günter, B. Zysset, M. Ahlheim, M. Stähelin, and F. Lehr, Macromolecules 27, 5476(1994).
[CrossRef]

Kuzyk, M. G.

Ledoux, I.

I. Ledoux and J. Zyss, Chem. Phys. 73, 203(1982).
[CrossRef]

Lee, V. Y.

C. R. Moylan, R. J. Twieg, V. Y. Lee, S. A. Swanson, K. M. Betterton, and R. D. Miller, J. Am. Chem. Soc. 115, 12599(1993).
[CrossRef]

Lehr, F.

P. Prêtre, P. Kaatz, A. Bohren, P. Günter, B. Zysset, M. Ahlheim, M. Stähelin, and F. Lehr, Macromolecules 27, 5476(1994).
[CrossRef]

Levine, B.

B. Levine and C. Bethea, Appl. Phys. Lett. 24, 445(1974).
[CrossRef]

Levine, B. F.

B. F. Levine and C. G. Bethea, J. Chem. Phys. 63, 2666(1975).
[CrossRef]

Man, H. T.

C. C. Teng and H. T. Man, Appl. Phys. Lett. 56, 1734(1990).
[CrossRef]

Marder, S. R.

M. Ahlheim, M. Barzoukas, P. V. Bedworth, M. Blanchard-Desce, A. Fort, Z.-Y. Hu, S. R. Marder, J. W. Perry, C. Runser, M. Stähelin, and B. Zysset, Science 271, 335(1996).
[CrossRef]

S. R. Marder, L.-T. Cheng, B. G. Tiemann, A. C. Friedli, M. Blanchard-Desce, J. W. Perry, and J. Skindhøj, Science 263, 511(1994).
[CrossRef] [PubMed]

Miller, R. D.

C. R. Moylan, R. J. Twieg, V. Y. Lee, S. A. Swanson, K. M. Betterton, and R. D. Miller, J. Am. Chem. Soc. 115, 12599(1993).
[CrossRef]

Moylan, C. R.

C. R. Moylan, R. J. Twieg, V. Y. Lee, S. A. Swanson, K. M. Betterton, and R. D. Miller, J. Am. Chem. Soc. 115, 12599(1993).
[CrossRef]

Oudar, J.-L.

J.-L. Oudar, J. Chem. Phys. 67, 446(1977).
[CrossRef]

Perry, J. W.

M. Ahlheim, M. Barzoukas, P. V. Bedworth, M. Blanchard-Desce, A. Fort, Z.-Y. Hu, S. R. Marder, J. W. Perry, C. Runser, M. Stähelin, and B. Zysset, Science 271, 335(1996).
[CrossRef]

S. R. Marder, L.-T. Cheng, B. G. Tiemann, A. C. Friedli, M. Blanchard-Desce, J. W. Perry, and J. Skindhøj, Science 263, 511(1994).
[CrossRef] [PubMed]

Prêtre, P.

P. Prêtre, P. Kaatz, A. Bohren, P. Günter, B. Zysset, M. Ahlheim, M. Stähelin, and F. Lehr, Macromolecules 27, 5476(1994).
[CrossRef]

Rao, V. P.

V. P. Rao, A. K-Y. Jen, K. Y. Wong, and K. J. Drost, J. Chem. Soc. Chem. Commun. 1118–1120(1993).
[CrossRef]

Rice, J. E.

A. Willetts, J. E. Rice, D. M. Burland, and D. P. Shelton, J. Chem. Phys. 97, 7590(1992).
[CrossRef]

Runser, C.

M. Ahlheim, M. Barzoukas, P. V. Bedworth, M. Blanchard-Desce, A. Fort, Z.-Y. Hu, S. R. Marder, J. W. Perry, C. Runser, M. Stähelin, and B. Zysset, Science 271, 335(1996).
[CrossRef]

Shelton, D. P.

A. Willetts, J. E. Rice, D. M. Burland, and D. P. Shelton, J. Chem. Phys. 97, 7590(1992).
[CrossRef]

Singer, K. D.

Skindhøj, J.

S. R. Marder, L.-T. Cheng, B. G. Tiemann, A. C. Friedli, M. Blanchard-Desce, J. W. Perry, and J. Skindhøj, Science 263, 511(1994).
[CrossRef] [PubMed]

Sohn, J. E.

Stähelin, M.

M. Ahlheim, M. Barzoukas, P. V. Bedworth, M. Blanchard-Desce, A. Fort, Z.-Y. Hu, S. R. Marder, J. W. Perry, C. Runser, M. Stähelin, and B. Zysset, Science 271, 335(1996).
[CrossRef]

P. Prêtre, P. Kaatz, A. Bohren, P. Günter, B. Zysset, M. Ahlheim, M. Stähelin, and F. Lehr, Macromolecules 27, 5476(1994).
[CrossRef]

Swanson, S. A.

C. R. Moylan, R. J. Twieg, V. Y. Lee, S. A. Swanson, K. M. Betterton, and R. D. Miller, J. Am. Chem. Soc. 115, 12599(1993).
[CrossRef]

Teng, C. C.

C. C. Teng and H. T. Man, Appl. Phys. Lett. 56, 1734(1990).
[CrossRef]

Tiemann, B. G.

S. R. Marder, L.-T. Cheng, B. G. Tiemann, A. C. Friedli, M. Blanchard-Desce, J. W. Perry, and J. Skindhøj, Science 263, 511(1994).
[CrossRef] [PubMed]

Twieg, R. J.

C. R. Moylan, R. J. Twieg, V. Y. Lee, S. A. Swanson, K. M. Betterton, and R. D. Miller, J. Am. Chem. Soc. 115, 12599(1993).
[CrossRef]

Willetts, A.

A. Willetts, J. E. Rice, D. M. Burland, and D. P. Shelton, J. Chem. Phys. 97, 7590(1992).
[CrossRef]

Wong, K. Y.

V. P. Rao, A. K-Y. Jen, K. Y. Wong, and K. J. Drost, J. Chem. Soc. Chem. Commun. 1118–1120(1993).
[CrossRef]

Zyss, J.

I. Ledoux and J. Zyss, Chem. Phys. 73, 203(1982).
[CrossRef]

Zysset, B.

M. Ahlheim, M. Barzoukas, P. V. Bedworth, M. Blanchard-Desce, A. Fort, Z.-Y. Hu, S. R. Marder, J. W. Perry, C. Runser, M. Stähelin, and B. Zysset, Science 271, 335(1996).
[CrossRef]

P. Prêtre, P. Kaatz, A. Bohren, P. Günter, B. Zysset, M. Ahlheim, M. Stähelin, and F. Lehr, Macromolecules 27, 5476(1994).
[CrossRef]

Appl. Phys. Lett.

B. Levine and C. Bethea, Appl. Phys. Lett. 24, 445(1974).
[CrossRef]

C. C. Teng and H. T. Man, Appl. Phys. Lett. 56, 1734(1990).
[CrossRef]

Chem. Phys.

I. Ledoux and J. Zyss, Chem. Phys. 73, 203(1982).
[CrossRef]

J. Am. Chem. Soc.

C. R. Moylan, R. J. Twieg, V. Y. Lee, S. A. Swanson, K. M. Betterton, and R. D. Miller, J. Am. Chem. Soc. 115, 12599(1993).
[CrossRef]

J. Chem. Phys.

A. Willetts, J. E. Rice, D. M. Burland, and D. P. Shelton, J. Chem. Phys. 97, 7590(1992).
[CrossRef]

J.-L. Oudar, J. Chem. Phys. 67, 446(1977).
[CrossRef]

B. F. Levine and C. G. Bethea, J. Chem. Phys. 63, 2666(1975).
[CrossRef]

J. Chem. Soc. Chem. Commun.

V. P. Rao, A. K-Y. Jen, K. Y. Wong, and K. J. Drost, J. Chem. Soc. Chem. Commun. 1118–1120(1993).
[CrossRef]

J. Opt. Soc. Am. B

Macromolecules

P. Prêtre, P. Kaatz, A. Bohren, P. Günter, B. Zysset, M. Ahlheim, M. Stähelin, and F. Lehr, Macromolecules 27, 5476(1994).
[CrossRef]

Science

M. Ahlheim, M. Barzoukas, P. V. Bedworth, M. Blanchard-Desce, A. Fort, Z.-Y. Hu, S. R. Marder, J. W. Perry, C. Runser, M. Stähelin, and B. Zysset, Science 271, 335(1996).
[CrossRef]

S. R. Marder, L.-T. Cheng, B. G. Tiemann, A. C. Friedli, M. Blanchard-Desce, J. W. Perry, and J. Skindhøj, Science 263, 511(1994).
[CrossRef] [PubMed]

Other

FORON® Blue is a registered trademark of SANDOZ Ltd., Basel, Switzerland.

British Patent GB 2026528 (1980); French Patent Fr 2438045 (1980). Both are held by Sandoz Ltd. (inventor, W. Baumann).

S. Akiyama, K. Nakashima, S. Nakatsuji, M. Suzuki, and C. Umekawa, Dyes Pigm. 8, 459 (1987).
[CrossRef]

R. Lemke, Synthesis (May 1974), p. 359.
[CrossRef]

C. W. Spangler and R. K. McCoy, Synth. Commun. 18, 51 (1988).
[CrossRef]

M. Ahlheim and F. Lehr, Macromol. Chem. Phys. 195, 361 (1994).
[CrossRef]

J. Zyss and D. Chemla, in Nonlinear Optical Properties of Organic Molecules and Crystals, Vol. 1 of Quadratic Nonlinear Optics, D. S. Chemla and J. Zyss, eds. (Academic, New York, 1987), p. 23.
[CrossRef]

J. Messier, F. Kajzar, C. Sentheim, M. Barzoukas, J. Zyss, M. Blanchard-Desce, and J. Lehn, Nonlinear Opt. 2, 53 (1992).

B. Zysset, M. Ahlheim, M. Stähelin, F. Lehr, P. Prêtre, P. Kaatz, and P. Günter, in Nonlinear Optical Properties of Organic Materials VI, G. R. Möhlmann, ed., Proc. SPIE 2025, 70 (1993).
[CrossRef]

C. R. Moylan, S. A. Swanson, C. A. Walsh, J. I. Thackara, R. J. Twieg, R. D. Miller, and V. Y. Lee, in Nonlinear Optical Properties of Organic Materials VI, G. R. Möhlmann, ed., Proc. SPIE 2025, 192 (1993).
[CrossRef]

L. Cheng, W. Tam, G. Meredith, G. Rikken, and E. Meijer, Nonlinear Optical Properties of Organic Materials II, G. Khanarian, ed., Proc. SPIE 1147, 61 (1990).
[CrossRef]

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Figures (8)

Fig. 1
Fig. 1

Structure and route of synthesis of push–pull polyenes with thiobarbituric acid (TBA) and 3-dicyanomethylene-2,3-dihydrobenzothiophene-1,1-dioxide (FB) acceptors. R denotes C2H5 (5a), C2H5 (7a), C6H5 (7b), C2H5 (9a), C6H5 (9b), C2H5 (11a), and C6H5 (11b).

Fig. 2
Fig. 2

Highly soluble di-n-buthyl analog of molecule 10 in Fig. 1.

Fig. 3
Fig. 3

Structure of the chromophore Azo 1̲.

Fig. 4
Fig. 4

Structure of the side-chain polymer containing Azo chromophores.

Fig. 5
Fig. 5

Experimental setup for the electro-optic (EO) characterization of guest–host films.

Fig. 6
Fig. 6

EO coefficient at λ=1.313 µm versus chromophore loading of polycarbonate (PC) guest–host polymers.

Fig. 7
Fig. 7

EO coefficient versus poling field E of a guest–host polymer (11-wt % of molecule 6 dissolved in PC, with λ=1.313 µm).

Fig. 8
Fig. 8

Log–log plot of µβ(-ω;ω,0) versus absorption maximum λmax. All data are from EO measurements at λ=1.313 µm and normalized to the value of the chromophore Azo 1̲.

Tables (4)

Tables Icon

Table 1 Results of Electro-Optical (EO) Measurements on Guest–Host Films Containing the Chromophore Azo 1̲ and Comparison with EO Measurements on the Azo-Containing Side-Chain Polymer (λ=1.31 µm)

Tables Icon

Table 2 Measured r-Values of PC–Guest–Host Thin Films Measured at λ=1.31 µma

Tables Icon

Table 3 Nonlinear Optical Properties of Polyenes with Thiobarbituric Acid (TBA) as Acceptor

Tables Icon

Table 4 Nonlinear Optical Properties of Novel Polyenes with 3-Dicyanomethylene-2,3-Dihydrobenzothiopene-1,1-Dioxide (FB) as Acceptor

Equations (6)

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

γ0=γe(-2ω;ω,ω,0)+μβ(-2ω;ω,ω)5kT,
βi(2ω)=jβijj(2ω).
r33=2Nfμβ(-ω;ω,ω,0)5kTn4E,
μβ(-ω;ω,0)relative=μβ(-2ω;ω,ω)(μβ)7a(-2ω;ω,ω)fEOfEFISH.
fEO=[1-(λmax,PC7a)2/λ2]23-(λmax,PC7a)2/λ23-λmax,PC2/λ2[1-(λmax,PC)2/λ2]2.
fEFISH=1-(λmax,solv)2/λ21-(λmax,solv7a)2/λ21-4(λmax,solv)2/λ21-4(λmax,solv7a)2/λ2.

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