Abstract

Lightguides were fabricated from three commercial polyimides of which one contains one and the others contain two hexafluoroisopropylidene (6F) groups. The latter are isomers using either the para or the meta isomer of the same diamine. As the number of 6F groups increases the optical losses of the corresponding lightguides decreases. In thick lightguides of the two 6F groups containing polyimides, loss values below 0.1 dB/cm can be realized using optimized conditions. Two mechanisms—ordering with or without charge transfer complex formation and voids or pinholes—are seen to be responsible for optical losses. The second type of losses can be reduced by cure optimization. Where ordering is possible annealing leads to increased optical losses. Geometrical restraint of the ordering, however, leads to loss reduction in otherwise identical conditions. Losses observed in the bulk are always higher than in the top and bottom layers of the polyimide films.

© 1988 Optical Society of America

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  1. R. Schriever, H. Franke, H. G. Festl, E. Kratzig, “Optical Waveguiding in Doped Poly(Methyl Methacrylate),” Polymer 26, 1423 (1985).
    [CrossRef]
  2. W. J. Tomlinson, E. A. Chandross, “Organic Photochemical Refractive Index Image Recording Systems,” Adv. Photochem. 12, 201 (1980).
    [CrossRef]
  3. T. Kurokawa, N. Takato, T. Katayama, “Polymer Optical Circuits for Multimode Optical Fiber Systems,” Appl. Opt. 19, 3124 (1980).
    [CrossRef] [PubMed]
  4. H. Franke, “Optical Recording of Refractive-Index Patterns in Doped Poly-(Methyl Methacrylate) Films,” Appl. Opt. 23, 2729 (1984).
    [CrossRef] [PubMed]
  5. M. J. Brekner, C. Feger, “Curing Studies of a Polyimide Precursor,” J. Polym. Sci. Polym. Chem. Ed. 25, 2005 (1987).
    [CrossRef]
  6. M. J. Brekner, C. Feger, “Curing Studies of a Polyimide Precursor. II. Polyamic Acid,” J. Polym. Sci. Polyin. Chem. Ed. 25, 2479 (1987).
    [CrossRef]
  7. C. Feger, “Curing of Polyimides,” Soc. Plast. Eng. Tech. Pap. 33, 967 (1987).
  8. N. Takahashi, D. Y. Yoon, W. Parrish, “Molecular Order in Condensed States of Semiflexible Poly(Amic Acid) and Polyimide,” Macromolecules 17, 2583 (1984).
    [CrossRef]
  9. T. P. Russell, “A Small Angle X-Ray Scattering Study of an Aromatic Polyimide,” J. Polym. Sci. Polym. Phys. Ed. 22, 1105 (1984).
    [CrossRef]
  10. T. P. Russell, H. Gugger, J. D. Swalen, “Inplane Orientation of Polyimide,” J. Polym. Sci. Polym. Ed. 21, 1745 (1983).
    [CrossRef]
  11. T. A. Gordina, B. V. Kotov, O. V. Kolninov, A. N. Pravednikov, “Charge Transfer Complexes of Certain Aromatic Polyimides,” Vysokomol. Soedin. Ser. B 15, 378 (1973).
  12. K. Furuya, B. I. Miller, L. A. Choldren, R. E. Howard, “Novel Deposit Spin Waveguide Interconnection (DSWI) Technique for Semiconductor Integrated Optics,” Electron. Lett. 18, 204 (1982).
    [CrossRef]
  13. H. Franke, G. Knabke, R. Reuter, “Lightguiding in Polyimide II,” Proc. Soc. Photo-Opt. Instrum. Eng. 682, 191 (1986).
  14. Du Pont, Pyralin product information.
  15. American Hoechst Co., SIXEF product information.
  16. R. Mathisen, E. Pyun, C. S. P. Sung, “Application of Dye Labelling in Polyimide Cure Studies,” Soc. Plast. Eng. Tech. Pap 33, 1103 (1987).
  17. J. Shouli, Y. Ligang, Z. Zikang, Z. Zhiming, Z. Qiyi, “Heat Treatment Study on Polyimide,” Conf. Rec. 1985 Intl. Conf. Prop. Appl. Dielectr. Mat. 2, 583 (1985).
  18. C. E. Diener, J. R. Susko, “Etching of Partially Cured Polyimide,” in Polyimides, K. L. Mittal, Ed. (Plenum, New York, 1984), p. 353.
  19. C. Feger, unpublished results.

1987

M. J. Brekner, C. Feger, “Curing Studies of a Polyimide Precursor,” J. Polym. Sci. Polym. Chem. Ed. 25, 2005 (1987).
[CrossRef]

M. J. Brekner, C. Feger, “Curing Studies of a Polyimide Precursor. II. Polyamic Acid,” J. Polym. Sci. Polyin. Chem. Ed. 25, 2479 (1987).
[CrossRef]

C. Feger, “Curing of Polyimides,” Soc. Plast. Eng. Tech. Pap. 33, 967 (1987).

R. Mathisen, E. Pyun, C. S. P. Sung, “Application of Dye Labelling in Polyimide Cure Studies,” Soc. Plast. Eng. Tech. Pap 33, 1103 (1987).

1986

H. Franke, G. Knabke, R. Reuter, “Lightguiding in Polyimide II,” Proc. Soc. Photo-Opt. Instrum. Eng. 682, 191 (1986).

1985

J. Shouli, Y. Ligang, Z. Zikang, Z. Zhiming, Z. Qiyi, “Heat Treatment Study on Polyimide,” Conf. Rec. 1985 Intl. Conf. Prop. Appl. Dielectr. Mat. 2, 583 (1985).

R. Schriever, H. Franke, H. G. Festl, E. Kratzig, “Optical Waveguiding in Doped Poly(Methyl Methacrylate),” Polymer 26, 1423 (1985).
[CrossRef]

1984

N. Takahashi, D. Y. Yoon, W. Parrish, “Molecular Order in Condensed States of Semiflexible Poly(Amic Acid) and Polyimide,” Macromolecules 17, 2583 (1984).
[CrossRef]

T. P. Russell, “A Small Angle X-Ray Scattering Study of an Aromatic Polyimide,” J. Polym. Sci. Polym. Phys. Ed. 22, 1105 (1984).
[CrossRef]

H. Franke, “Optical Recording of Refractive-Index Patterns in Doped Poly-(Methyl Methacrylate) Films,” Appl. Opt. 23, 2729 (1984).
[CrossRef] [PubMed]

1983

T. P. Russell, H. Gugger, J. D. Swalen, “Inplane Orientation of Polyimide,” J. Polym. Sci. Polym. Ed. 21, 1745 (1983).
[CrossRef]

1982

K. Furuya, B. I. Miller, L. A. Choldren, R. E. Howard, “Novel Deposit Spin Waveguide Interconnection (DSWI) Technique for Semiconductor Integrated Optics,” Electron. Lett. 18, 204 (1982).
[CrossRef]

1980

W. J. Tomlinson, E. A. Chandross, “Organic Photochemical Refractive Index Image Recording Systems,” Adv. Photochem. 12, 201 (1980).
[CrossRef]

T. Kurokawa, N. Takato, T. Katayama, “Polymer Optical Circuits for Multimode Optical Fiber Systems,” Appl. Opt. 19, 3124 (1980).
[CrossRef] [PubMed]

1973

T. A. Gordina, B. V. Kotov, O. V. Kolninov, A. N. Pravednikov, “Charge Transfer Complexes of Certain Aromatic Polyimides,” Vysokomol. Soedin. Ser. B 15, 378 (1973).

Brekner, M. J.

M. J. Brekner, C. Feger, “Curing Studies of a Polyimide Precursor,” J. Polym. Sci. Polym. Chem. Ed. 25, 2005 (1987).
[CrossRef]

M. J. Brekner, C. Feger, “Curing Studies of a Polyimide Precursor. II. Polyamic Acid,” J. Polym. Sci. Polyin. Chem. Ed. 25, 2479 (1987).
[CrossRef]

Chandross, E. A.

W. J. Tomlinson, E. A. Chandross, “Organic Photochemical Refractive Index Image Recording Systems,” Adv. Photochem. 12, 201 (1980).
[CrossRef]

Choldren, L. A.

K. Furuya, B. I. Miller, L. A. Choldren, R. E. Howard, “Novel Deposit Spin Waveguide Interconnection (DSWI) Technique for Semiconductor Integrated Optics,” Electron. Lett. 18, 204 (1982).
[CrossRef]

Diener, C. E.

C. E. Diener, J. R. Susko, “Etching of Partially Cured Polyimide,” in Polyimides, K. L. Mittal, Ed. (Plenum, New York, 1984), p. 353.

Feger, C.

C. Feger, “Curing of Polyimides,” Soc. Plast. Eng. Tech. Pap. 33, 967 (1987).

M. J. Brekner, C. Feger, “Curing Studies of a Polyimide Precursor. II. Polyamic Acid,” J. Polym. Sci. Polyin. Chem. Ed. 25, 2479 (1987).
[CrossRef]

M. J. Brekner, C. Feger, “Curing Studies of a Polyimide Precursor,” J. Polym. Sci. Polym. Chem. Ed. 25, 2005 (1987).
[CrossRef]

C. Feger, unpublished results.

Festl, H. G.

R. Schriever, H. Franke, H. G. Festl, E. Kratzig, “Optical Waveguiding in Doped Poly(Methyl Methacrylate),” Polymer 26, 1423 (1985).
[CrossRef]

Franke, H.

H. Franke, G. Knabke, R. Reuter, “Lightguiding in Polyimide II,” Proc. Soc. Photo-Opt. Instrum. Eng. 682, 191 (1986).

R. Schriever, H. Franke, H. G. Festl, E. Kratzig, “Optical Waveguiding in Doped Poly(Methyl Methacrylate),” Polymer 26, 1423 (1985).
[CrossRef]

H. Franke, “Optical Recording of Refractive-Index Patterns in Doped Poly-(Methyl Methacrylate) Films,” Appl. Opt. 23, 2729 (1984).
[CrossRef] [PubMed]

Furuya, K.

K. Furuya, B. I. Miller, L. A. Choldren, R. E. Howard, “Novel Deposit Spin Waveguide Interconnection (DSWI) Technique for Semiconductor Integrated Optics,” Electron. Lett. 18, 204 (1982).
[CrossRef]

Gordina, T. A.

T. A. Gordina, B. V. Kotov, O. V. Kolninov, A. N. Pravednikov, “Charge Transfer Complexes of Certain Aromatic Polyimides,” Vysokomol. Soedin. Ser. B 15, 378 (1973).

Gugger, H.

T. P. Russell, H. Gugger, J. D. Swalen, “Inplane Orientation of Polyimide,” J. Polym. Sci. Polym. Ed. 21, 1745 (1983).
[CrossRef]

Howard, R. E.

K. Furuya, B. I. Miller, L. A. Choldren, R. E. Howard, “Novel Deposit Spin Waveguide Interconnection (DSWI) Technique for Semiconductor Integrated Optics,” Electron. Lett. 18, 204 (1982).
[CrossRef]

Katayama, T.

Knabke, G.

H. Franke, G. Knabke, R. Reuter, “Lightguiding in Polyimide II,” Proc. Soc. Photo-Opt. Instrum. Eng. 682, 191 (1986).

Kolninov, O. V.

T. A. Gordina, B. V. Kotov, O. V. Kolninov, A. N. Pravednikov, “Charge Transfer Complexes of Certain Aromatic Polyimides,” Vysokomol. Soedin. Ser. B 15, 378 (1973).

Kotov, B. V.

T. A. Gordina, B. V. Kotov, O. V. Kolninov, A. N. Pravednikov, “Charge Transfer Complexes of Certain Aromatic Polyimides,” Vysokomol. Soedin. Ser. B 15, 378 (1973).

Kratzig, E.

R. Schriever, H. Franke, H. G. Festl, E. Kratzig, “Optical Waveguiding in Doped Poly(Methyl Methacrylate),” Polymer 26, 1423 (1985).
[CrossRef]

Kurokawa, T.

Ligang, Y.

J. Shouli, Y. Ligang, Z. Zikang, Z. Zhiming, Z. Qiyi, “Heat Treatment Study on Polyimide,” Conf. Rec. 1985 Intl. Conf. Prop. Appl. Dielectr. Mat. 2, 583 (1985).

Mathisen, R.

R. Mathisen, E. Pyun, C. S. P. Sung, “Application of Dye Labelling in Polyimide Cure Studies,” Soc. Plast. Eng. Tech. Pap 33, 1103 (1987).

Miller, B. I.

K. Furuya, B. I. Miller, L. A. Choldren, R. E. Howard, “Novel Deposit Spin Waveguide Interconnection (DSWI) Technique for Semiconductor Integrated Optics,” Electron. Lett. 18, 204 (1982).
[CrossRef]

Parrish, W.

N. Takahashi, D. Y. Yoon, W. Parrish, “Molecular Order in Condensed States of Semiflexible Poly(Amic Acid) and Polyimide,” Macromolecules 17, 2583 (1984).
[CrossRef]

Pravednikov, A. N.

T. A. Gordina, B. V. Kotov, O. V. Kolninov, A. N. Pravednikov, “Charge Transfer Complexes of Certain Aromatic Polyimides,” Vysokomol. Soedin. Ser. B 15, 378 (1973).

Pyun, E.

R. Mathisen, E. Pyun, C. S. P. Sung, “Application of Dye Labelling in Polyimide Cure Studies,” Soc. Plast. Eng. Tech. Pap 33, 1103 (1987).

Qiyi, Z.

J. Shouli, Y. Ligang, Z. Zikang, Z. Zhiming, Z. Qiyi, “Heat Treatment Study on Polyimide,” Conf. Rec. 1985 Intl. Conf. Prop. Appl. Dielectr. Mat. 2, 583 (1985).

Reuter, R.

H. Franke, G. Knabke, R. Reuter, “Lightguiding in Polyimide II,” Proc. Soc. Photo-Opt. Instrum. Eng. 682, 191 (1986).

Russell, T. P.

T. P. Russell, “A Small Angle X-Ray Scattering Study of an Aromatic Polyimide,” J. Polym. Sci. Polym. Phys. Ed. 22, 1105 (1984).
[CrossRef]

T. P. Russell, H. Gugger, J. D. Swalen, “Inplane Orientation of Polyimide,” J. Polym. Sci. Polym. Ed. 21, 1745 (1983).
[CrossRef]

Schriever, R.

R. Schriever, H. Franke, H. G. Festl, E. Kratzig, “Optical Waveguiding in Doped Poly(Methyl Methacrylate),” Polymer 26, 1423 (1985).
[CrossRef]

Shouli, J.

J. Shouli, Y. Ligang, Z. Zikang, Z. Zhiming, Z. Qiyi, “Heat Treatment Study on Polyimide,” Conf. Rec. 1985 Intl. Conf. Prop. Appl. Dielectr. Mat. 2, 583 (1985).

Sung, C. S. P.

R. Mathisen, E. Pyun, C. S. P. Sung, “Application of Dye Labelling in Polyimide Cure Studies,” Soc. Plast. Eng. Tech. Pap 33, 1103 (1987).

Susko, J. R.

C. E. Diener, J. R. Susko, “Etching of Partially Cured Polyimide,” in Polyimides, K. L. Mittal, Ed. (Plenum, New York, 1984), p. 353.

Swalen, J. D.

T. P. Russell, H. Gugger, J. D. Swalen, “Inplane Orientation of Polyimide,” J. Polym. Sci. Polym. Ed. 21, 1745 (1983).
[CrossRef]

Takahashi, N.

N. Takahashi, D. Y. Yoon, W. Parrish, “Molecular Order in Condensed States of Semiflexible Poly(Amic Acid) and Polyimide,” Macromolecules 17, 2583 (1984).
[CrossRef]

Takato, N.

Tomlinson, W. J.

W. J. Tomlinson, E. A. Chandross, “Organic Photochemical Refractive Index Image Recording Systems,” Adv. Photochem. 12, 201 (1980).
[CrossRef]

Yoon, D. Y.

N. Takahashi, D. Y. Yoon, W. Parrish, “Molecular Order in Condensed States of Semiflexible Poly(Amic Acid) and Polyimide,” Macromolecules 17, 2583 (1984).
[CrossRef]

Zhiming, Z.

J. Shouli, Y. Ligang, Z. Zikang, Z. Zhiming, Z. Qiyi, “Heat Treatment Study on Polyimide,” Conf. Rec. 1985 Intl. Conf. Prop. Appl. Dielectr. Mat. 2, 583 (1985).

Zikang, Z.

J. Shouli, Y. Ligang, Z. Zikang, Z. Zhiming, Z. Qiyi, “Heat Treatment Study on Polyimide,” Conf. Rec. 1985 Intl. Conf. Prop. Appl. Dielectr. Mat. 2, 583 (1985).

Adv. Photochem.

W. J. Tomlinson, E. A. Chandross, “Organic Photochemical Refractive Index Image Recording Systems,” Adv. Photochem. 12, 201 (1980).
[CrossRef]

Appl. Opt.

Conf. Rec. 1985 Intl. Conf. Prop. Appl. Dielectr. Mat.

J. Shouli, Y. Ligang, Z. Zikang, Z. Zhiming, Z. Qiyi, “Heat Treatment Study on Polyimide,” Conf. Rec. 1985 Intl. Conf. Prop. Appl. Dielectr. Mat. 2, 583 (1985).

Electron. Lett.

K. Furuya, B. I. Miller, L. A. Choldren, R. E. Howard, “Novel Deposit Spin Waveguide Interconnection (DSWI) Technique for Semiconductor Integrated Optics,” Electron. Lett. 18, 204 (1982).
[CrossRef]

J. Polym. Sci. Polyin. Chem. Ed.

M. J. Brekner, C. Feger, “Curing Studies of a Polyimide Precursor. II. Polyamic Acid,” J. Polym. Sci. Polyin. Chem. Ed. 25, 2479 (1987).
[CrossRef]

J. Polym. Sci. Polym. Chem. Ed.

M. J. Brekner, C. Feger, “Curing Studies of a Polyimide Precursor,” J. Polym. Sci. Polym. Chem. Ed. 25, 2005 (1987).
[CrossRef]

J. Polym. Sci. Polym. Ed.

T. P. Russell, H. Gugger, J. D. Swalen, “Inplane Orientation of Polyimide,” J. Polym. Sci. Polym. Ed. 21, 1745 (1983).
[CrossRef]

J. Polym. Sci. Polym. Phys. Ed.

T. P. Russell, “A Small Angle X-Ray Scattering Study of an Aromatic Polyimide,” J. Polym. Sci. Polym. Phys. Ed. 22, 1105 (1984).
[CrossRef]

Macromolecules

N. Takahashi, D. Y. Yoon, W. Parrish, “Molecular Order in Condensed States of Semiflexible Poly(Amic Acid) and Polyimide,” Macromolecules 17, 2583 (1984).
[CrossRef]

Polymer

R. Schriever, H. Franke, H. G. Festl, E. Kratzig, “Optical Waveguiding in Doped Poly(Methyl Methacrylate),” Polymer 26, 1423 (1985).
[CrossRef]

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

H. Franke, G. Knabke, R. Reuter, “Lightguiding in Polyimide II,” Proc. Soc. Photo-Opt. Instrum. Eng. 682, 191 (1986).

Soc. Plast. Eng. Tech. Pap

R. Mathisen, E. Pyun, C. S. P. Sung, “Application of Dye Labelling in Polyimide Cure Studies,” Soc. Plast. Eng. Tech. Pap 33, 1103 (1987).

Soc. Plast. Eng. Tech. Pap.

C. Feger, “Curing of Polyimides,” Soc. Plast. Eng. Tech. Pap. 33, 967 (1987).

Vysokomol. Soedin. Ser. B

T. A. Gordina, B. V. Kotov, O. V. Kolninov, A. N. Pravednikov, “Charge Transfer Complexes of Certain Aromatic Polyimides,” Vysokomol. Soedin. Ser. B 15, 378 (1973).

Other

C. E. Diener, J. R. Susko, “Etching of Partially Cured Polyimide,” in Polyimides, K. L. Mittal, Ed. (Plenum, New York, 1984), p. 353.

C. Feger, unpublished results.

Du Pont, Pyralin product information.

American Hoechst Co., SIXEF product information.

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Figures (10)

Fig. 1
Fig. 1

Molecular structure of polyimides (a) HFDA-ODA; (b) HFDA-HFDAM-4,4; and (c) HFDA-HFDAM-33.

Fig. 2
Fig. 2

DMTA spectra of the cure of HFDA-ODA: (a) at 5°C/min; (b) at 0.5°C/min; and (c) fully cured.

Fig. 3
Fig. 3

Refractive indices of HFDA-ODA films measured for parallel (□) and perpendicular (△) polarized light vs maximum cure temperature of the polyimide. The filled symbols represent the respective refractive indices of an isothermally (1.5 h at 300°C) cured film.

Fig. 4
Fig. 4

Total optical loss (average values for the first three modes) of fast cured HFDA-ODA film (t > 3.5 μm) vs maximum cure temperature. The symbols are the same as in Fig. 3.

Fig. 5
Fig. 5

Absorption spectra of an HFDA-ODA polyimide film (t = 12 μm) on glass as a function of the annealing procedure. Slow heating was employed.

Fig. 6
Fig. 6

Total optical loss of HFDA-ODA film (t = 3.5 μm) cured to 220°C as a function of the mode number.

Fig. 7
Fig. 7

Optical loss values of zero-order modes for thick (t > 3.5 μm; open symbols) and thin (t < 1.5 μm; filled symbols) planar waveguides of HFDA-ODA on glass as a function of the refractive index of parallel polarized light nTE.

Fig. 8
Fig. 8

DMTA spectra of the cure of HFDA-HFDAM-44 (a) at 5°C/min; (b) at 0.5 °C/min (… …, fully cured); (c) sample previously heated to 250°C.

Fig. 9
Fig. 9

Optical loss for zero-order modes of HFDA-HFDA as a function of anneal time: HFDA-HFDAM-44 at 200°C (●) and 300°C (■); HFDA-HFDAM-33 at 300°C (▲).

Fig. 10
Fig. 10

Absorption spectra of HFDA-HFDAM-44 polyimide film (t = 5 μm) on glass as a function of annealing procedures and heating rates (<20°C/min: s.c.; 100°C/min: r.c.)

Tables (1)

Tables Icon

Table I Refractive Indices of the Investigated Polylmides After Drying and Fully Cured

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