Abstract

We tested the use of two hydrophobic methyl-substituted silane precursors, methyltriethoxysilane and dimethyldiethoxysilane, to synthesize methyl-modified silica sols by a two-step method and a cohydrolysis method to produce durable antireflective films with high laser-induced-damage thresholds (LIDTs). Using small-angle x-ray scattering technology, we obtained details of the microstructure of clusters in sol and found various double fractal structural characteristics in the methyl-modified silica clusters; our findings were confirmed by transmission-electron micrographs. Through a  29Si magic-angle spin nuclear magnetic resonance study of the corresponding xerogels, we determined the double-fractal microstructure, which we then related to the LIDTs of AR films. The distribution configuration of methyls in clusters determined the double-fractal microstructure of clusters and then the LIDTs of AR films. The LIDTs of films produced by the cohydrolysis method (the highest was 38 J/cm2 for 1-ns, 1064-nm laser action) were much higher than those from the two-step method because of the loose netlike clusters in the former configuration. During the 220-day aging, the transmittance of hydrophobic AR film decreased ∼0.2%. So it is practicable to prepare durable AR films with higher LIDTs than those of normal AR SiO2 films only by introducing hydrophobic methyls into a Si–O–Si matrix of clusters if an appropriate hydrophobic precursor is chosen.

© 2005 Optical Society of America

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  1. H. G. Floch and P. F. Belleville, "Optical thin films from the sol-gel process," in Optical Interference Coatings, F. Abeles, ed., Proc. SPIE 2253, 764-790 (1994).
    [CrossRef]
  2. D. R. Uhlmann, J. M. Boulton, G. Teowee, L. Weisenbach, and B. J. J. Zelinski, "Sol-gel synthesis of optical thin films and coatings," in Sol-Gel Optics, J. D. Mackenzie and D. K. Ulrich, eds., Proc. SPIE 1328, 270-294 (1990).
    [CrossRef]
  3. H. G. Floch, P. F. Belleville, and P. M. Pegon, "Sol-gel optical coatings for lasers. II," Bull. Am. Ceram. Soc. 74, 84-89 (1995).
  4. H. A. Mcinnes, J. E. Andrew, N. J. Bazin, A. J. Morris, and K. J. Porter, "Ultra violet laser damage and optical properties of high refractive index single layers, multiple layers and high/low index multilayer stacks," in Laser-Induced Damage in Optical Materials: 1997, G. J. Exarhos, A. H. Guenther, M. K. Kozlowski, and M. J. Soileau, eds., Proc. SPIE 3244, 500-508 (1998).
    [CrossRef]
  5. W. Stöber, A. Fink, and E. Bohn, "Controlled growth of monodisperse silica spheres on the micro size range," J. Colloid Interface Sci. 26, 62-66 (1968).
    [CrossRef]
  6. K. Tadanaga, N. Katata, and T. Minami, "Formation process of super-water-repellent Al2O3 coating films with high transparency by the sol-gel method," J. Am. Ceram. Soc. 80, 3213-3216 (1997).
    [CrossRef]
  7. T. Minami, N. Katata, and K. Tadanaga, "Preparation and characterization of super water-repellent Al2O3 coating films with high transparency," in Sol-Gel Optics IV, B. S. Dunn, J. D. Mackenzie, E. J. Pope, H. K. Schmidt, and M. Yanane, eds., Proc. SPIE 3136, 168-175 (1997).
    [CrossRef]
  8. T. Nakagawa and M. Soga, "A new method for fabricating water repellent silica films having high heat-resistance using the sol-gel method," J. Non-Cryst. Solids 260, 167-174 (1999).
    [CrossRef]
  9. B. S. Hong, J. H. Han, S. T. Kim, M. S. Park, T. Dolukhanyan, and C. Sung, "Durable water-repellent glass for automobiles," Thin Solid Films 351, 274-278 (1999).
    [CrossRef]
  10. A. Nakajima, K. Abe, K. Hashimoto, and T. Watanabe, "Preparation of hard super-hydrophobic films with visible light transmission," Thin Solid Films 376, 140-143 (2000).
    [CrossRef]
  11. K. Tadanaga, J. Morinaga, and T. Minami, "Superhydrophobic-superhydrophilic micropatterning on flowerlike alumina coating film by the sol-gel method," Chem. Mater. 12, 590-592 (2000).
    [CrossRef]
  12. K. Ogawa, M. Soga, Y. Takada, and I. Nakayama, "Development of a transparent and ultrahydrophobic glass plate," Jpn. J. Appl. Phys. 32, 614-615 (1993).
    [CrossRef]
  13. Y. Aksmatsu, K. Makita, H. Inaba, and T. Minami, "Water-repellent coating films on glass prepared from hydrolysis and polycondensation reactions of fluoroalkyltrialkoxylsilane," Thin Solid Films 389, 138-145 (2001).
    [CrossRef]
  14. M. Morra, E. Occhiehho, and F. Garbassi, "Contact angle hysteresis in oxygen plasma treated poly(tetrafluoroethylene)," Langmuir 5, 872-876 (1989).
    [CrossRef]
  15. C. J. Brinker and G. W. Scherer, Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing (Academic, San Diego, Calif., 1990), pp. 160-173.
  16. Ref. 15 , pp. 97-99.
  17. B. M. De Witte, D. Commers, and J. B. Uytterhoeven, "Distribution of organic groups in silica gels prepared from organo-alkoxysilanes," J. Non-Cryst. Solids 202, 35-41 (1996).
    [CrossRef]
  18. Z. Y. Zhang and H. Wakabayashi, "Structural study of Al(acac)3 catalyzed CH3SiO3/2 gel," J. Sol-Gel Sci. Technol. 12, 153-158 (1998).
    [CrossRef]
  19. C. A. Capozzi, L. D. Pye, and R. A. S. Condrate, "Vibrational spectral/structural changes from the hydrolysis/polycondensation of methyl-modified silicates. I. Comparisons for single monomer condensates," Mater. Lett. 15, 130-136 (1992).
    [CrossRef]
  20. S. Yoshiyuki, O. Seigo, and K. Kazuyuki, "29Si NMR study of hydrolysis and initial polycondensation processes of organoalkoxysilanes. I. Dimethyldiethoxysilane," J. Non-Cryst. Solids 139, 25-34 (1992).
    [CrossRef]
  21. R. Zhang, Y. Xü, Q. H. Meng, J. Wang, H. Zhao, and B. Z. Dong, "Small angle x-ray scattering study of microstructure changes of organic hydrogels from supercritical carbon dioxide drying," J. Supercrit. Fluids 28, 263-276 (2004).
    [CrossRef]
  22. Y. Xu, Z. H. Li, W. H. Fan, D. Wu, Y. H. Sun, L. X. Rong, and B. Z. Dong, "Density fluctuation in silica-PVA hybrid gels determined by small-angle x-ray scattering," Appl. Surf. Sci. 225, 126-133 (2004).
    [CrossRef]
  23. Y. Xu, Z. H. Li, W. H. Fan, D. Wu, Y. H. Sun, L. X. Rong, and B. Z. Dong, "Two fractal structures of methyl-modified silica gels by SAXS," Acta Phys. Sin. 52, 442-447 (2003).
  24. C. Mutter, T. N. M. Bernards, and M. P. J. Peeters, "The effect of the solvent on the cross-link density of SiO2 coatings," Thin Solid Films 351, 95-98 (1999).
    [CrossRef]
  25. K. D. Keefer and D. W. Schaefer, "Growth of fractally rough colloids," Phys. Rev. Lett. 56, 2376-2379 (1986).
    [CrossRef] [PubMed]
  26. A. F. Craievich, "SAXS study of the porous fractal structure of tricalcuim silicate dry gels," J. Appl. Crystallogr. 20, 327-329 (1987).
    [CrossRef]
  27. C. Marliere, F. Despetis, P. Etienne, and J. Phalippou, "Two fractal structures in aerogel," J. Non-Cryst. Solids 285, 175-180 (2001).
    [CrossRef]

2004 (2)

R. Zhang, Y. Xü, Q. H. Meng, J. Wang, H. Zhao, and B. Z. Dong, "Small angle x-ray scattering study of microstructure changes of organic hydrogels from supercritical carbon dioxide drying," J. Supercrit. Fluids 28, 263-276 (2004).
[CrossRef]

Y. Xu, Z. H. Li, W. H. Fan, D. Wu, Y. H. Sun, L. X. Rong, and B. Z. Dong, "Density fluctuation in silica-PVA hybrid gels determined by small-angle x-ray scattering," Appl. Surf. Sci. 225, 126-133 (2004).
[CrossRef]

2003 (1)

Y. Xu, Z. H. Li, W. H. Fan, D. Wu, Y. H. Sun, L. X. Rong, and B. Z. Dong, "Two fractal structures of methyl-modified silica gels by SAXS," Acta Phys. Sin. 52, 442-447 (2003).

2001 (2)

C. Marliere, F. Despetis, P. Etienne, and J. Phalippou, "Two fractal structures in aerogel," J. Non-Cryst. Solids 285, 175-180 (2001).
[CrossRef]

Y. Aksmatsu, K. Makita, H. Inaba, and T. Minami, "Water-repellent coating films on glass prepared from hydrolysis and polycondensation reactions of fluoroalkyltrialkoxylsilane," Thin Solid Films 389, 138-145 (2001).
[CrossRef]

2000 (2)

A. Nakajima, K. Abe, K. Hashimoto, and T. Watanabe, "Preparation of hard super-hydrophobic films with visible light transmission," Thin Solid Films 376, 140-143 (2000).
[CrossRef]

K. Tadanaga, J. Morinaga, and T. Minami, "Superhydrophobic-superhydrophilic micropatterning on flowerlike alumina coating film by the sol-gel method," Chem. Mater. 12, 590-592 (2000).
[CrossRef]

1999 (3)

T. Nakagawa and M. Soga, "A new method for fabricating water repellent silica films having high heat-resistance using the sol-gel method," J. Non-Cryst. Solids 260, 167-174 (1999).
[CrossRef]

B. S. Hong, J. H. Han, S. T. Kim, M. S. Park, T. Dolukhanyan, and C. Sung, "Durable water-repellent glass for automobiles," Thin Solid Films 351, 274-278 (1999).
[CrossRef]

C. Mutter, T. N. M. Bernards, and M. P. J. Peeters, "The effect of the solvent on the cross-link density of SiO2 coatings," Thin Solid Films 351, 95-98 (1999).
[CrossRef]

1998 (2)

H. A. Mcinnes, J. E. Andrew, N. J. Bazin, A. J. Morris, and K. J. Porter, "Ultra violet laser damage and optical properties of high refractive index single layers, multiple layers and high/low index multilayer stacks," in Laser-Induced Damage in Optical Materials: 1997, G. J. Exarhos, A. H. Guenther, M. K. Kozlowski, and M. J. Soileau, eds., Proc. SPIE 3244, 500-508 (1998).
[CrossRef]

Z. Y. Zhang and H. Wakabayashi, "Structural study of Al(acac)3 catalyzed CH3SiO3/2 gel," J. Sol-Gel Sci. Technol. 12, 153-158 (1998).
[CrossRef]

1997 (2)

K. Tadanaga, N. Katata, and T. Minami, "Formation process of super-water-repellent Al2O3 coating films with high transparency by the sol-gel method," J. Am. Ceram. Soc. 80, 3213-3216 (1997).
[CrossRef]

T. Minami, N. Katata, and K. Tadanaga, "Preparation and characterization of super water-repellent Al2O3 coating films with high transparency," in Sol-Gel Optics IV, B. S. Dunn, J. D. Mackenzie, E. J. Pope, H. K. Schmidt, and M. Yanane, eds., Proc. SPIE 3136, 168-175 (1997).
[CrossRef]

1996 (1)

B. M. De Witte, D. Commers, and J. B. Uytterhoeven, "Distribution of organic groups in silica gels prepared from organo-alkoxysilanes," J. Non-Cryst. Solids 202, 35-41 (1996).
[CrossRef]

1995 (1)

H. G. Floch, P. F. Belleville, and P. M. Pegon, "Sol-gel optical coatings for lasers. II," Bull. Am. Ceram. Soc. 74, 84-89 (1995).

1994 (1)

H. G. Floch and P. F. Belleville, "Optical thin films from the sol-gel process," in Optical Interference Coatings, F. Abeles, ed., Proc. SPIE 2253, 764-790 (1994).
[CrossRef]

1993 (1)

K. Ogawa, M. Soga, Y. Takada, and I. Nakayama, "Development of a transparent and ultrahydrophobic glass plate," Jpn. J. Appl. Phys. 32, 614-615 (1993).
[CrossRef]

1992 (2)

C. A. Capozzi, L. D. Pye, and R. A. S. Condrate, "Vibrational spectral/structural changes from the hydrolysis/polycondensation of methyl-modified silicates. I. Comparisons for single monomer condensates," Mater. Lett. 15, 130-136 (1992).
[CrossRef]

S. Yoshiyuki, O. Seigo, and K. Kazuyuki, "29Si NMR study of hydrolysis and initial polycondensation processes of organoalkoxysilanes. I. Dimethyldiethoxysilane," J. Non-Cryst. Solids 139, 25-34 (1992).
[CrossRef]

1990 (1)

D. R. Uhlmann, J. M. Boulton, G. Teowee, L. Weisenbach, and B. J. J. Zelinski, "Sol-gel synthesis of optical thin films and coatings," in Sol-Gel Optics, J. D. Mackenzie and D. K. Ulrich, eds., Proc. SPIE 1328, 270-294 (1990).
[CrossRef]

1989 (1)

M. Morra, E. Occhiehho, and F. Garbassi, "Contact angle hysteresis in oxygen plasma treated poly(tetrafluoroethylene)," Langmuir 5, 872-876 (1989).
[CrossRef]

1987 (1)

A. F. Craievich, "SAXS study of the porous fractal structure of tricalcuim silicate dry gels," J. Appl. Crystallogr. 20, 327-329 (1987).
[CrossRef]

1986 (1)

K. D. Keefer and D. W. Schaefer, "Growth of fractally rough colloids," Phys. Rev. Lett. 56, 2376-2379 (1986).
[CrossRef] [PubMed]

1968 (1)

W. Stöber, A. Fink, and E. Bohn, "Controlled growth of monodisperse silica spheres on the micro size range," J. Colloid Interface Sci. 26, 62-66 (1968).
[CrossRef]

Abe, K.

A. Nakajima, K. Abe, K. Hashimoto, and T. Watanabe, "Preparation of hard super-hydrophobic films with visible light transmission," Thin Solid Films 376, 140-143 (2000).
[CrossRef]

Aksmatsu, Y.

Y. Aksmatsu, K. Makita, H. Inaba, and T. Minami, "Water-repellent coating films on glass prepared from hydrolysis and polycondensation reactions of fluoroalkyltrialkoxylsilane," Thin Solid Films 389, 138-145 (2001).
[CrossRef]

Andrew, J. E.

H. A. Mcinnes, J. E. Andrew, N. J. Bazin, A. J. Morris, and K. J. Porter, "Ultra violet laser damage and optical properties of high refractive index single layers, multiple layers and high/low index multilayer stacks," in Laser-Induced Damage in Optical Materials: 1997, G. J. Exarhos, A. H. Guenther, M. K. Kozlowski, and M. J. Soileau, eds., Proc. SPIE 3244, 500-508 (1998).
[CrossRef]

Bazin, N. J.

H. A. Mcinnes, J. E. Andrew, N. J. Bazin, A. J. Morris, and K. J. Porter, "Ultra violet laser damage and optical properties of high refractive index single layers, multiple layers and high/low index multilayer stacks," in Laser-Induced Damage in Optical Materials: 1997, G. J. Exarhos, A. H. Guenther, M. K. Kozlowski, and M. J. Soileau, eds., Proc. SPIE 3244, 500-508 (1998).
[CrossRef]

Belleville, P. F.

H. G. Floch, P. F. Belleville, and P. M. Pegon, "Sol-gel optical coatings for lasers. II," Bull. Am. Ceram. Soc. 74, 84-89 (1995).

H. G. Floch and P. F. Belleville, "Optical thin films from the sol-gel process," in Optical Interference Coatings, F. Abeles, ed., Proc. SPIE 2253, 764-790 (1994).
[CrossRef]

Bernards, T. N. M.

C. Mutter, T. N. M. Bernards, and M. P. J. Peeters, "The effect of the solvent on the cross-link density of SiO2 coatings," Thin Solid Films 351, 95-98 (1999).
[CrossRef]

Bohn, E.

W. Stöber, A. Fink, and E. Bohn, "Controlled growth of monodisperse silica spheres on the micro size range," J. Colloid Interface Sci. 26, 62-66 (1968).
[CrossRef]

Boulton, J. M.

D. R. Uhlmann, J. M. Boulton, G. Teowee, L. Weisenbach, and B. J. J. Zelinski, "Sol-gel synthesis of optical thin films and coatings," in Sol-Gel Optics, J. D. Mackenzie and D. K. Ulrich, eds., Proc. SPIE 1328, 270-294 (1990).
[CrossRef]

Capozzi, C. A.

C. A. Capozzi, L. D. Pye, and R. A. S. Condrate, "Vibrational spectral/structural changes from the hydrolysis/polycondensation of methyl-modified silicates. I. Comparisons for single monomer condensates," Mater. Lett. 15, 130-136 (1992).
[CrossRef]

Commers, D.

B. M. De Witte, D. Commers, and J. B. Uytterhoeven, "Distribution of organic groups in silica gels prepared from organo-alkoxysilanes," J. Non-Cryst. Solids 202, 35-41 (1996).
[CrossRef]

Condrate, R. A. S.

C. A. Capozzi, L. D. Pye, and R. A. S. Condrate, "Vibrational spectral/structural changes from the hydrolysis/polycondensation of methyl-modified silicates. I. Comparisons for single monomer condensates," Mater. Lett. 15, 130-136 (1992).
[CrossRef]

Craievich, A. F.

A. F. Craievich, "SAXS study of the porous fractal structure of tricalcuim silicate dry gels," J. Appl. Crystallogr. 20, 327-329 (1987).
[CrossRef]

De Witte, B. M.

B. M. De Witte, D. Commers, and J. B. Uytterhoeven, "Distribution of organic groups in silica gels prepared from organo-alkoxysilanes," J. Non-Cryst. Solids 202, 35-41 (1996).
[CrossRef]

Despetis, F.

C. Marliere, F. Despetis, P. Etienne, and J. Phalippou, "Two fractal structures in aerogel," J. Non-Cryst. Solids 285, 175-180 (2001).
[CrossRef]

Dolukhanyan, T.

B. S. Hong, J. H. Han, S. T. Kim, M. S. Park, T. Dolukhanyan, and C. Sung, "Durable water-repellent glass for automobiles," Thin Solid Films 351, 274-278 (1999).
[CrossRef]

Dong, B. Z.

R. Zhang, Y. Xü, Q. H. Meng, J. Wang, H. Zhao, and B. Z. Dong, "Small angle x-ray scattering study of microstructure changes of organic hydrogels from supercritical carbon dioxide drying," J. Supercrit. Fluids 28, 263-276 (2004).
[CrossRef]

Y. Xu, Z. H. Li, W. H. Fan, D. Wu, Y. H. Sun, L. X. Rong, and B. Z. Dong, "Density fluctuation in silica-PVA hybrid gels determined by small-angle x-ray scattering," Appl. Surf. Sci. 225, 126-133 (2004).
[CrossRef]

Y. Xu, Z. H. Li, W. H. Fan, D. Wu, Y. H. Sun, L. X. Rong, and B. Z. Dong, "Two fractal structures of methyl-modified silica gels by SAXS," Acta Phys. Sin. 52, 442-447 (2003).

Etienne, P.

C. Marliere, F. Despetis, P. Etienne, and J. Phalippou, "Two fractal structures in aerogel," J. Non-Cryst. Solids 285, 175-180 (2001).
[CrossRef]

Fan, W. H.

Y. Xu, Z. H. Li, W. H. Fan, D. Wu, Y. H. Sun, L. X. Rong, and B. Z. Dong, "Density fluctuation in silica-PVA hybrid gels determined by small-angle x-ray scattering," Appl. Surf. Sci. 225, 126-133 (2004).
[CrossRef]

Y. Xu, Z. H. Li, W. H. Fan, D. Wu, Y. H. Sun, L. X. Rong, and B. Z. Dong, "Two fractal structures of methyl-modified silica gels by SAXS," Acta Phys. Sin. 52, 442-447 (2003).

Fink, A.

W. Stöber, A. Fink, and E. Bohn, "Controlled growth of monodisperse silica spheres on the micro size range," J. Colloid Interface Sci. 26, 62-66 (1968).
[CrossRef]

Floch, H. G.

H. G. Floch, P. F. Belleville, and P. M. Pegon, "Sol-gel optical coatings for lasers. II," Bull. Am. Ceram. Soc. 74, 84-89 (1995).

Floch , H. G.

H. G. Floch and P. F. Belleville, "Optical thin films from the sol-gel process," in Optical Interference Coatings, F. Abeles, ed., Proc. SPIE 2253, 764-790 (1994).
[CrossRef]

Garbassi, F.

M. Morra, E. Occhiehho, and F. Garbassi, "Contact angle hysteresis in oxygen plasma treated poly(tetrafluoroethylene)," Langmuir 5, 872-876 (1989).
[CrossRef]

Han, J. H.

B. S. Hong, J. H. Han, S. T. Kim, M. S. Park, T. Dolukhanyan, and C. Sung, "Durable water-repellent glass for automobiles," Thin Solid Films 351, 274-278 (1999).
[CrossRef]

Hashimoto, K.

A. Nakajima, K. Abe, K. Hashimoto, and T. Watanabe, "Preparation of hard super-hydrophobic films with visible light transmission," Thin Solid Films 376, 140-143 (2000).
[CrossRef]

Hong, B. S.

B. S. Hong, J. H. Han, S. T. Kim, M. S. Park, T. Dolukhanyan, and C. Sung, "Durable water-repellent glass for automobiles," Thin Solid Films 351, 274-278 (1999).
[CrossRef]

Inaba, H.

Y. Aksmatsu, K. Makita, H. Inaba, and T. Minami, "Water-repellent coating films on glass prepared from hydrolysis and polycondensation reactions of fluoroalkyltrialkoxylsilane," Thin Solid Films 389, 138-145 (2001).
[CrossRef]

Katata, N.

K. Tadanaga, N. Katata, and T. Minami, "Formation process of super-water-repellent Al2O3 coating films with high transparency by the sol-gel method," J. Am. Ceram. Soc. 80, 3213-3216 (1997).
[CrossRef]

T. Minami, N. Katata, and K. Tadanaga, "Preparation and characterization of super water-repellent Al2O3 coating films with high transparency," in Sol-Gel Optics IV, B. S. Dunn, J. D. Mackenzie, E. J. Pope, H. K. Schmidt, and M. Yanane, eds., Proc. SPIE 3136, 168-175 (1997).
[CrossRef]

Kazuyuki, K.

S. Yoshiyuki, O. Seigo, and K. Kazuyuki, "29Si NMR study of hydrolysis and initial polycondensation processes of organoalkoxysilanes. I. Dimethyldiethoxysilane," J. Non-Cryst. Solids 139, 25-34 (1992).
[CrossRef]

Keefer , K. D.

K. D. Keefer and D. W. Schaefer, "Growth of fractally rough colloids," Phys. Rev. Lett. 56, 2376-2379 (1986).
[CrossRef] [PubMed]

Kim, S. T.

B. S. Hong, J. H. Han, S. T. Kim, M. S. Park, T. Dolukhanyan, and C. Sung, "Durable water-repellent glass for automobiles," Thin Solid Films 351, 274-278 (1999).
[CrossRef]

Li, Z. H.

Y. Xu, Z. H. Li, W. H. Fan, D. Wu, Y. H. Sun, L. X. Rong, and B. Z. Dong, "Density fluctuation in silica-PVA hybrid gels determined by small-angle x-ray scattering," Appl. Surf. Sci. 225, 126-133 (2004).
[CrossRef]

Y. Xu, Z. H. Li, W. H. Fan, D. Wu, Y. H. Sun, L. X. Rong, and B. Z. Dong, "Two fractal structures of methyl-modified silica gels by SAXS," Acta Phys. Sin. 52, 442-447 (2003).

Makita, K.

Y. Aksmatsu, K. Makita, H. Inaba, and T. Minami, "Water-repellent coating films on glass prepared from hydrolysis and polycondensation reactions of fluoroalkyltrialkoxylsilane," Thin Solid Films 389, 138-145 (2001).
[CrossRef]

Marliere, C.

C. Marliere, F. Despetis, P. Etienne, and J. Phalippou, "Two fractal structures in aerogel," J. Non-Cryst. Solids 285, 175-180 (2001).
[CrossRef]

Mcinnes, H. A.

H. A. Mcinnes, J. E. Andrew, N. J. Bazin, A. J. Morris, and K. J. Porter, "Ultra violet laser damage and optical properties of high refractive index single layers, multiple layers and high/low index multilayer stacks," in Laser-Induced Damage in Optical Materials: 1997, G. J. Exarhos, A. H. Guenther, M. K. Kozlowski, and M. J. Soileau, eds., Proc. SPIE 3244, 500-508 (1998).
[CrossRef]

Meng, Q. H.

R. Zhang, Y. Xü, Q. H. Meng, J. Wang, H. Zhao, and B. Z. Dong, "Small angle x-ray scattering study of microstructure changes of organic hydrogels from supercritical carbon dioxide drying," J. Supercrit. Fluids 28, 263-276 (2004).
[CrossRef]

Minami, T.

Y. Aksmatsu, K. Makita, H. Inaba, and T. Minami, "Water-repellent coating films on glass prepared from hydrolysis and polycondensation reactions of fluoroalkyltrialkoxylsilane," Thin Solid Films 389, 138-145 (2001).
[CrossRef]

K. Tadanaga, J. Morinaga, and T. Minami, "Superhydrophobic-superhydrophilic micropatterning on flowerlike alumina coating film by the sol-gel method," Chem. Mater. 12, 590-592 (2000).
[CrossRef]

K. Tadanaga, N. Katata, and T. Minami, "Formation process of super-water-repellent Al2O3 coating films with high transparency by the sol-gel method," J. Am. Ceram. Soc. 80, 3213-3216 (1997).
[CrossRef]

T. Minami, N. Katata, and K. Tadanaga, "Preparation and characterization of super water-repellent Al2O3 coating films with high transparency," in Sol-Gel Optics IV, B. S. Dunn, J. D. Mackenzie, E. J. Pope, H. K. Schmidt, and M. Yanane, eds., Proc. SPIE 3136, 168-175 (1997).
[CrossRef]

Morinaga, J.

K. Tadanaga, J. Morinaga, and T. Minami, "Superhydrophobic-superhydrophilic micropatterning on flowerlike alumina coating film by the sol-gel method," Chem. Mater. 12, 590-592 (2000).
[CrossRef]

Morra, M.

M. Morra, E. Occhiehho, and F. Garbassi, "Contact angle hysteresis in oxygen plasma treated poly(tetrafluoroethylene)," Langmuir 5, 872-876 (1989).
[CrossRef]

Morris, A. J.

H. A. Mcinnes, J. E. Andrew, N. J. Bazin, A. J. Morris, and K. J. Porter, "Ultra violet laser damage and optical properties of high refractive index single layers, multiple layers and high/low index multilayer stacks," in Laser-Induced Damage in Optical Materials: 1997, G. J. Exarhos, A. H. Guenther, M. K. Kozlowski, and M. J. Soileau, eds., Proc. SPIE 3244, 500-508 (1998).
[CrossRef]

Mutter, C.

C. Mutter, T. N. M. Bernards, and M. P. J. Peeters, "The effect of the solvent on the cross-link density of SiO2 coatings," Thin Solid Films 351, 95-98 (1999).
[CrossRef]

Nakagawa , T.

T. Nakagawa and M. Soga, "A new method for fabricating water repellent silica films having high heat-resistance using the sol-gel method," J. Non-Cryst. Solids 260, 167-174 (1999).
[CrossRef]

Nakajima, A.

A. Nakajima, K. Abe, K. Hashimoto, and T. Watanabe, "Preparation of hard super-hydrophobic films with visible light transmission," Thin Solid Films 376, 140-143 (2000).
[CrossRef]

Nakayama, I.

K. Ogawa, M. Soga, Y. Takada, and I. Nakayama, "Development of a transparent and ultrahydrophobic glass plate," Jpn. J. Appl. Phys. 32, 614-615 (1993).
[CrossRef]

Occhiehho, E.

M. Morra, E. Occhiehho, and F. Garbassi, "Contact angle hysteresis in oxygen plasma treated poly(tetrafluoroethylene)," Langmuir 5, 872-876 (1989).
[CrossRef]

Ogawa, K.

K. Ogawa, M. Soga, Y. Takada, and I. Nakayama, "Development of a transparent and ultrahydrophobic glass plate," Jpn. J. Appl. Phys. 32, 614-615 (1993).
[CrossRef]

Park, M. S.

B. S. Hong, J. H. Han, S. T. Kim, M. S. Park, T. Dolukhanyan, and C. Sung, "Durable water-repellent glass for automobiles," Thin Solid Films 351, 274-278 (1999).
[CrossRef]

Peeters, M. P. J.

C. Mutter, T. N. M. Bernards, and M. P. J. Peeters, "The effect of the solvent on the cross-link density of SiO2 coatings," Thin Solid Films 351, 95-98 (1999).
[CrossRef]

Pegon, P. M.

H. G. Floch, P. F. Belleville, and P. M. Pegon, "Sol-gel optical coatings for lasers. II," Bull. Am. Ceram. Soc. 74, 84-89 (1995).

Phalippou, J.

C. Marliere, F. Despetis, P. Etienne, and J. Phalippou, "Two fractal structures in aerogel," J. Non-Cryst. Solids 285, 175-180 (2001).
[CrossRef]

Porter, K. J.

H. A. Mcinnes, J. E. Andrew, N. J. Bazin, A. J. Morris, and K. J. Porter, "Ultra violet laser damage and optical properties of high refractive index single layers, multiple layers and high/low index multilayer stacks," in Laser-Induced Damage in Optical Materials: 1997, G. J. Exarhos, A. H. Guenther, M. K. Kozlowski, and M. J. Soileau, eds., Proc. SPIE 3244, 500-508 (1998).
[CrossRef]

Pye, L. D.

C. A. Capozzi, L. D. Pye, and R. A. S. Condrate, "Vibrational spectral/structural changes from the hydrolysis/polycondensation of methyl-modified silicates. I. Comparisons for single monomer condensates," Mater. Lett. 15, 130-136 (1992).
[CrossRef]

Rong, L. X.

Y. Xu, Z. H. Li, W. H. Fan, D. Wu, Y. H. Sun, L. X. Rong, and B. Z. Dong, "Density fluctuation in silica-PVA hybrid gels determined by small-angle x-ray scattering," Appl. Surf. Sci. 225, 126-133 (2004).
[CrossRef]

Y. Xu, Z. H. Li, W. H. Fan, D. Wu, Y. H. Sun, L. X. Rong, and B. Z. Dong, "Two fractal structures of methyl-modified silica gels by SAXS," Acta Phys. Sin. 52, 442-447 (2003).

Schaefer, D. W.

K. D. Keefer and D. W. Schaefer, "Growth of fractally rough colloids," Phys. Rev. Lett. 56, 2376-2379 (1986).
[CrossRef] [PubMed]

Seigo, O.

S. Yoshiyuki, O. Seigo, and K. Kazuyuki, "29Si NMR study of hydrolysis and initial polycondensation processes of organoalkoxysilanes. I. Dimethyldiethoxysilane," J. Non-Cryst. Solids 139, 25-34 (1992).
[CrossRef]

Soga, M.

T. Nakagawa and M. Soga, "A new method for fabricating water repellent silica films having high heat-resistance using the sol-gel method," J. Non-Cryst. Solids 260, 167-174 (1999).
[CrossRef]

K. Ogawa, M. Soga, Y. Takada, and I. Nakayama, "Development of a transparent and ultrahydrophobic glass plate," Jpn. J. Appl. Phys. 32, 614-615 (1993).
[CrossRef]

Stöber, W.

W. Stöber, A. Fink, and E. Bohn, "Controlled growth of monodisperse silica spheres on the micro size range," J. Colloid Interface Sci. 26, 62-66 (1968).
[CrossRef]

Sun, Y. H.

Y. Xu, Z. H. Li, W. H. Fan, D. Wu, Y. H. Sun, L. X. Rong, and B. Z. Dong, "Density fluctuation in silica-PVA hybrid gels determined by small-angle x-ray scattering," Appl. Surf. Sci. 225, 126-133 (2004).
[CrossRef]

Y. Xu, Z. H. Li, W. H. Fan, D. Wu, Y. H. Sun, L. X. Rong, and B. Z. Dong, "Two fractal structures of methyl-modified silica gels by SAXS," Acta Phys. Sin. 52, 442-447 (2003).

Sung, C.

B. S. Hong, J. H. Han, S. T. Kim, M. S. Park, T. Dolukhanyan, and C. Sung, "Durable water-repellent glass for automobiles," Thin Solid Films 351, 274-278 (1999).
[CrossRef]

Tadanaga, K.

K. Tadanaga, J. Morinaga, and T. Minami, "Superhydrophobic-superhydrophilic micropatterning on flowerlike alumina coating film by the sol-gel method," Chem. Mater. 12, 590-592 (2000).
[CrossRef]

T. Minami, N. Katata, and K. Tadanaga, "Preparation and characterization of super water-repellent Al2O3 coating films with high transparency," in Sol-Gel Optics IV, B. S. Dunn, J. D. Mackenzie, E. J. Pope, H. K. Schmidt, and M. Yanane, eds., Proc. SPIE 3136, 168-175 (1997).
[CrossRef]

K. Tadanaga, N. Katata, and T. Minami, "Formation process of super-water-repellent Al2O3 coating films with high transparency by the sol-gel method," J. Am. Ceram. Soc. 80, 3213-3216 (1997).
[CrossRef]

Takada, Y.

K. Ogawa, M. Soga, Y. Takada, and I. Nakayama, "Development of a transparent and ultrahydrophobic glass plate," Jpn. J. Appl. Phys. 32, 614-615 (1993).
[CrossRef]

Teowee, G.

D. R. Uhlmann, J. M. Boulton, G. Teowee, L. Weisenbach, and B. J. J. Zelinski, "Sol-gel synthesis of optical thin films and coatings," in Sol-Gel Optics, J. D. Mackenzie and D. K. Ulrich, eds., Proc. SPIE 1328, 270-294 (1990).
[CrossRef]

Uhlmann, D. R.

D. R. Uhlmann, J. M. Boulton, G. Teowee, L. Weisenbach, and B. J. J. Zelinski, "Sol-gel synthesis of optical thin films and coatings," in Sol-Gel Optics, J. D. Mackenzie and D. K. Ulrich, eds., Proc. SPIE 1328, 270-294 (1990).
[CrossRef]

Uytterhoeven, J. B.

B. M. De Witte, D. Commers, and J. B. Uytterhoeven, "Distribution of organic groups in silica gels prepared from organo-alkoxysilanes," J. Non-Cryst. Solids 202, 35-41 (1996).
[CrossRef]

Wakabayashi, H.

Z. Y. Zhang and H. Wakabayashi, "Structural study of Al(acac)3 catalyzed CH3SiO3/2 gel," J. Sol-Gel Sci. Technol. 12, 153-158 (1998).
[CrossRef]

Wang, J.

R. Zhang, Y. Xü, Q. H. Meng, J. Wang, H. Zhao, and B. Z. Dong, "Small angle x-ray scattering study of microstructure changes of organic hydrogels from supercritical carbon dioxide drying," J. Supercrit. Fluids 28, 263-276 (2004).
[CrossRef]

Watanabe, T.

A. Nakajima, K. Abe, K. Hashimoto, and T. Watanabe, "Preparation of hard super-hydrophobic films with visible light transmission," Thin Solid Films 376, 140-143 (2000).
[CrossRef]

Weisenbach, L.

D. R. Uhlmann, J. M. Boulton, G. Teowee, L. Weisenbach, and B. J. J. Zelinski, "Sol-gel synthesis of optical thin films and coatings," in Sol-Gel Optics, J. D. Mackenzie and D. K. Ulrich, eds., Proc. SPIE 1328, 270-294 (1990).
[CrossRef]

Wu, D.

Y. Xu, Z. H. Li, W. H. Fan, D. Wu, Y. H. Sun, L. X. Rong, and B. Z. Dong, "Density fluctuation in silica-PVA hybrid gels determined by small-angle x-ray scattering," Appl. Surf. Sci. 225, 126-133 (2004).
[CrossRef]

Y. Xu, Z. H. Li, W. H. Fan, D. Wu, Y. H. Sun, L. X. Rong, and B. Z. Dong, "Two fractal structures of methyl-modified silica gels by SAXS," Acta Phys. Sin. 52, 442-447 (2003).

Xu, Y.

Y. Xu, Z. H. Li, W. H. Fan, D. Wu, Y. H. Sun, L. X. Rong, and B. Z. Dong, "Density fluctuation in silica-PVA hybrid gels determined by small-angle x-ray scattering," Appl. Surf. Sci. 225, 126-133 (2004).
[CrossRef]

Y. Xu, Z. H. Li, W. H. Fan, D. Wu, Y. H. Sun, L. X. Rong, and B. Z. Dong, "Two fractal structures of methyl-modified silica gels by SAXS," Acta Phys. Sin. 52, 442-447 (2003).

Xü, Y.

R. Zhang, Y. Xü, Q. H. Meng, J. Wang, H. Zhao, and B. Z. Dong, "Small angle x-ray scattering study of microstructure changes of organic hydrogels from supercritical carbon dioxide drying," J. Supercrit. Fluids 28, 263-276 (2004).
[CrossRef]

Yoshiyuki, S.

S. Yoshiyuki, O. Seigo, and K. Kazuyuki, "29Si NMR study of hydrolysis and initial polycondensation processes of organoalkoxysilanes. I. Dimethyldiethoxysilane," J. Non-Cryst. Solids 139, 25-34 (1992).
[CrossRef]

Zelinski, B. J. J.

D. R. Uhlmann, J. M. Boulton, G. Teowee, L. Weisenbach, and B. J. J. Zelinski, "Sol-gel synthesis of optical thin films and coatings," in Sol-Gel Optics, J. D. Mackenzie and D. K. Ulrich, eds., Proc. SPIE 1328, 270-294 (1990).
[CrossRef]

Zhang, R.

R. Zhang, Y. Xü, Q. H. Meng, J. Wang, H. Zhao, and B. Z. Dong, "Small angle x-ray scattering study of microstructure changes of organic hydrogels from supercritical carbon dioxide drying," J. Supercrit. Fluids 28, 263-276 (2004).
[CrossRef]

Zhang , Z. Y.

Z. Y. Zhang and H. Wakabayashi, "Structural study of Al(acac)3 catalyzed CH3SiO3/2 gel," J. Sol-Gel Sci. Technol. 12, 153-158 (1998).
[CrossRef]

Zhao, H.

R. Zhang, Y. Xü, Q. H. Meng, J. Wang, H. Zhao, and B. Z. Dong, "Small angle x-ray scattering study of microstructure changes of organic hydrogels from supercritical carbon dioxide drying," J. Supercrit. Fluids 28, 263-276 (2004).
[CrossRef]

Acta Phys. Sin. (1)

Y. Xu, Z. H. Li, W. H. Fan, D. Wu, Y. H. Sun, L. X. Rong, and B. Z. Dong, "Two fractal structures of methyl-modified silica gels by SAXS," Acta Phys. Sin. 52, 442-447 (2003).

Appl. Surf. Sci. (1)

Y. Xu, Z. H. Li, W. H. Fan, D. Wu, Y. H. Sun, L. X. Rong, and B. Z. Dong, "Density fluctuation in silica-PVA hybrid gels determined by small-angle x-ray scattering," Appl. Surf. Sci. 225, 126-133 (2004).
[CrossRef]

Bull. Am. Ceram. Soc. (1)

H. G. Floch, P. F. Belleville, and P. M. Pegon, "Sol-gel optical coatings for lasers. II," Bull. Am. Ceram. Soc. 74, 84-89 (1995).

Chem. Mater. (1)

K. Tadanaga, J. Morinaga, and T. Minami, "Superhydrophobic-superhydrophilic micropatterning on flowerlike alumina coating film by the sol-gel method," Chem. Mater. 12, 590-592 (2000).
[CrossRef]

J. Am. Ceram. Soc. (1)

K. Tadanaga, N. Katata, and T. Minami, "Formation process of super-water-repellent Al2O3 coating films with high transparency by the sol-gel method," J. Am. Ceram. Soc. 80, 3213-3216 (1997).
[CrossRef]

J. Appl. Crystallogr. (1)

A. F. Craievich, "SAXS study of the porous fractal structure of tricalcuim silicate dry gels," J. Appl. Crystallogr. 20, 327-329 (1987).
[CrossRef]

J. Colloid Interface Sci. (1)

W. Stöber, A. Fink, and E. Bohn, "Controlled growth of monodisperse silica spheres on the micro size range," J. Colloid Interface Sci. 26, 62-66 (1968).
[CrossRef]

J. Non-Cryst. Solids (4)

C. Marliere, F. Despetis, P. Etienne, and J. Phalippou, "Two fractal structures in aerogel," J. Non-Cryst. Solids 285, 175-180 (2001).
[CrossRef]

T. Nakagawa and M. Soga, "A new method for fabricating water repellent silica films having high heat-resistance using the sol-gel method," J. Non-Cryst. Solids 260, 167-174 (1999).
[CrossRef]

B. M. De Witte, D. Commers, and J. B. Uytterhoeven, "Distribution of organic groups in silica gels prepared from organo-alkoxysilanes," J. Non-Cryst. Solids 202, 35-41 (1996).
[CrossRef]

S. Yoshiyuki, O. Seigo, and K. Kazuyuki, "29Si NMR study of hydrolysis and initial polycondensation processes of organoalkoxysilanes. I. Dimethyldiethoxysilane," J. Non-Cryst. Solids 139, 25-34 (1992).
[CrossRef]

J. Sol-Gel Sci. Technol. (1)

Z. Y. Zhang and H. Wakabayashi, "Structural study of Al(acac)3 catalyzed CH3SiO3/2 gel," J. Sol-Gel Sci. Technol. 12, 153-158 (1998).
[CrossRef]

J. Supercrit. Fluids (1)

R. Zhang, Y. Xü, Q. H. Meng, J. Wang, H. Zhao, and B. Z. Dong, "Small angle x-ray scattering study of microstructure changes of organic hydrogels from supercritical carbon dioxide drying," J. Supercrit. Fluids 28, 263-276 (2004).
[CrossRef]

Jpn. J. Appl. Phys. (1)

K. Ogawa, M. Soga, Y. Takada, and I. Nakayama, "Development of a transparent and ultrahydrophobic glass plate," Jpn. J. Appl. Phys. 32, 614-615 (1993).
[CrossRef]

Langmuir (1)

M. Morra, E. Occhiehho, and F. Garbassi, "Contact angle hysteresis in oxygen plasma treated poly(tetrafluoroethylene)," Langmuir 5, 872-876 (1989).
[CrossRef]

Mater. Lett. (1)

C. A. Capozzi, L. D. Pye, and R. A. S. Condrate, "Vibrational spectral/structural changes from the hydrolysis/polycondensation of methyl-modified silicates. I. Comparisons for single monomer condensates," Mater. Lett. 15, 130-136 (1992).
[CrossRef]

Phys. Rev. Lett. (1)

K. D. Keefer and D. W. Schaefer, "Growth of fractally rough colloids," Phys. Rev. Lett. 56, 2376-2379 (1986).
[CrossRef] [PubMed]

Proc. SPIE (4)

T. Minami, N. Katata, and K. Tadanaga, "Preparation and characterization of super water-repellent Al2O3 coating films with high transparency," in Sol-Gel Optics IV, B. S. Dunn, J. D. Mackenzie, E. J. Pope, H. K. Schmidt, and M. Yanane, eds., Proc. SPIE 3136, 168-175 (1997).
[CrossRef]

H. A. Mcinnes, J. E. Andrew, N. J. Bazin, A. J. Morris, and K. J. Porter, "Ultra violet laser damage and optical properties of high refractive index single layers, multiple layers and high/low index multilayer stacks," in Laser-Induced Damage in Optical Materials: 1997, G. J. Exarhos, A. H. Guenther, M. K. Kozlowski, and M. J. Soileau, eds., Proc. SPIE 3244, 500-508 (1998).
[CrossRef]

H. G. Floch and P. F. Belleville, "Optical thin films from the sol-gel process," in Optical Interference Coatings, F. Abeles, ed., Proc. SPIE 2253, 764-790 (1994).
[CrossRef]

D. R. Uhlmann, J. M. Boulton, G. Teowee, L. Weisenbach, and B. J. J. Zelinski, "Sol-gel synthesis of optical thin films and coatings," in Sol-Gel Optics, J. D. Mackenzie and D. K. Ulrich, eds., Proc. SPIE 1328, 270-294 (1990).
[CrossRef]

Thin Solid Films (4)

B. S. Hong, J. H. Han, S. T. Kim, M. S. Park, T. Dolukhanyan, and C. Sung, "Durable water-repellent glass for automobiles," Thin Solid Films 351, 274-278 (1999).
[CrossRef]

A. Nakajima, K. Abe, K. Hashimoto, and T. Watanabe, "Preparation of hard super-hydrophobic films with visible light transmission," Thin Solid Films 376, 140-143 (2000).
[CrossRef]

Y. Aksmatsu, K. Makita, H. Inaba, and T. Minami, "Water-repellent coating films on glass prepared from hydrolysis and polycondensation reactions of fluoroalkyltrialkoxylsilane," Thin Solid Films 389, 138-145 (2001).
[CrossRef]

C. Mutter, T. N. M. Bernards, and M. P. J. Peeters, "The effect of the solvent on the cross-link density of SiO2 coatings," Thin Solid Films 351, 95-98 (1999).
[CrossRef]

Other (2)

C. J. Brinker and G. W. Scherer, Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing (Academic, San Diego, Calif., 1990), pp. 160-173.

Ref. 15 , pp. 97-99.

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Figures (9)

Fig. 1
Fig. 1

Schematic of optics for testing the LIDT. B, C, calorimeter and photodiode, respectively; M1, M2, mirrors.

Fig. 2
Fig. 2

Transmittance of hydrophobic AR films versus x; x is the molar percentage of hydrophobic precursor.

Fig. 3
Fig. 3

Water–film contact angle versus x; x is the molar percentage of hydrophobic precursor.

Fig. 4
Fig. 4

AFM morphologies of hydrophobic AR films. Rq is the average roughness in the direction perpendicular to the surface.

Fig. 5
Fig. 5

Laser-induced damage morphologies of hydrophobic AR films. The magnification is 28.

Fig. 6
Fig. 6

Durability of films.

Fig. 7
Fig. 7

 29Si MAS-NMR results for xerogels: ppm, parts in 106.

Fig. 8
Fig. 8

Transmission-electron microscope photographs of modified and unmodified SiO2 sols.

Fig. 9
Fig. 9

Differential scanning calorimetry thermal analysis results of xerogels.

Tables (3)

Tables Icon

Table 1 Components of Solsa

Tables Icon

Table 3 Results Obtained from SAXSa

Metrics