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Inorganic Sol—Gel Glasses as Matrices for Nonlinear Optical Materials Downloaded by UNIV OF CALIFORNIA SANTA BARBARA on September 1, 2015 | http://pubs.acs.org Publication Date: March 11, 1991 | doi: 10.1021/bk-1991-0455.ch036
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Jeffrey I. Zink , Bruce Dunn , R. B. Kaner , Ε. T. Knobbe , and J. McKiernan 1
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Department of Chemistry and Biochemistry and Department of Materials Science and Engineering, University of California, Los Angeles, CA 90024
Sol-gel synthesis of inorganic glasses offers a low temperature route to the microencapsulation of organic and organometallic molecules in inorganic matrices. The encapsulated molecules can be used to induce new optical properties in the material or to probe the changes at the molecular level which occur during the polymerization, aging and drying of the glass. Two different aspects of non-linear optical properties induced in the glass are discussed here. First, laser dyes including rhodamines and coumarins are encapsulated. The resulting doped gel-glasses exhibit optical gain and laser action. The non-linear response to the pulse energy of the pump laser as well as other optical characteristics of these new solid-state lasers will be discussed. Second, encapsulation of 2-ethylpolyaniline has been achieved. Degenerate four-wave mixing studies have been carried out, but the observed signal cannot be unambiguously attributed to χ effects. (3)
The sol-gel process is a solution synthesis technique which provides a low temperature chemical route for the preparation of rigid, transparent matrix materials (1-8). A wide variety of organic and organometallic molecules have been incorporated, via the sol-gel technique, into S1O2, AI2O3-S1O2 and organically modified silicate (ORMOSIL) host matrices (1-8). The focus of this paper is the encapsulation of organic laser dye molecules to produce new optical materials which exhibit optical gain and laser action, and of soluble polyaniline to produce new materials having potentially large third-order susceptibilities. In the first part of this paper, we report the results of our studies of laser action. The three types of host materials mentioned above are used to encapsulate coumarin and rhodamine laser dyes. The synthesis of the doped gels and gel-glasses is reported. The results of our studies of optical gain, laser spectral output, the output energy dependence on the pump pulse energy, and stability are discussed. The characteristics of the three types of hosts and their effects on laser action are compared. In the second part of this paper, we report the results of our studies of incorporation of 2-ethylpolyaniline in S1O2 gels. The results of a degenerate four wave mixing study are presented and discussed.
0097-6156/91A)455- 99% Τ over 1 mm pathlength) for the C S 2 reference and 4 cm" (96% Τ over 1 mm pathlength) for the 2-Et PANi doped silica film. The reflectivity of the doped gel was found to be 31% of that from the C S 2 reference. Assuming that the third-order susceptibility of carbon disulfide is 1.7 χ 10" esu at 1.06 μπι, and assuming that the entire signal arises from third order susceptibility effects, χ ( ) of the polyaniline doped gel was calculated to be 4.8 x 10~ esu (6.7 x 1 0 m / V ) . However, a number of effects including thermal effects could contribute to the observed signal and we cannot unambiguously attribute the observed signal to χΟ). The delay of the peak response of the doped gel with respect of CS2 by about 3-4 nsec suggests that thermal effects could be important. 4
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In Materials for Nonlinear Optics; Marder, S., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1991.
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MATERIALS FOR NONLINEAR OPTICS: CHEMICAL PERSPECTIVES
Downloaded by UNIV OF CALIFORNIA SANTA BARBARA on September 1, 2015 | http://pubs.acs.org Publication Date: March 11, 1991 | doi: 10.1021/bk-1991-0455.ch036
Acknowledgments The support of the National Science Foundation (DMR 87-06010) is gratefully acknowledged. Literature Cited 1. Mackenzie, J. D.; Ulrich, D. R., eds. Proc. Third Intnl. Conf. on Ultrastructure Processing Wiley, New York, 1988. 2. McKiernan, J.; Pouxviel, J.-C.; Dunn, B.; Zink, J. I. J. Phys. Chem. 1989, 22, 2129. 3. Pouxviel, J.C.;Dunn, B.; Zink, J. I. J. Phys. Chem. 1989,93,2134. 4. Kaufman, V.; Avnir, D. Langmuir 1986, 2, 717. 5. Avnir, D.; Levy, D.; Reisfeld, R. J. Phys. Chem. 1984, 88, 5956. 6. Avnir, D.; Kaufman, V. R.; Reisfeld. R. J. Non-Cryst. Solids, 1985, 74, 395. 7. Kaufman, V. R. Avnir, D.; Pines-Rojanski, D.; Huppert, D. J. Non-Cryst. Solids 1988, 99, 379. 8. Pouxviel, J.C.;Boilot, J. P.; Lecomte, Α.; Dauger, A. J. Phys. (Paris) 1987, 48, 921. 9. Esquivas, L.; Zarzycki, J. Proc. Third Intnl. Conf. on Ultrastructure Processing of Ceramics. Glasses, and Composites. Mackenzie, J. D. and Ulrich, D. R., Eds., Wiley Interscience, 1988. 10. Capozzi, C. Α.; Pye, L. D. Proc. SPIE. 1988, 970. 11. Schmidt, H.; Seiferling, B. MRS Symp. Proc. 1986, 73, 739. 12. Jones, G.; Jackson, W. R., Halpern, A. M. Chem. Phys. Lett. 1980,72,391. 13. Itoh, U.; Takakusa, M.; Moriya, T.; Saito, S. Jap. J. Appl. Phys., 1977, 16, 1059. 14. Gromov, D. Α.; Dyumaev, Κ. M.; Manenkov, Α. Α.; Maslyukov, A. P.; Matyushin, G. Α.; Nechitailo, V. S.; Prokhorov, A. M. J. Opt. Soc. Am. B. 1985, 2, 1028. 15. Leclerc, M.; Guay, J.; Ho, L. H. Macromolecules. 1989, 22, 649. 16. MacDiarmid, A. G.; Chiang, J.C.;Halpern, M.; Huang, W. S. Mol. Cryst. Liq. Cryst. 1985, 121, 173. 17. Cushman, R. J.; McManus, P. M.; Yang, S. C. J. Electroanal. Chem. 1986, 291. 335. 18. Yariv, Α.; Fisher, R. A. Optical Phase Conjugation: Fisher, R. Α., ed. Academic Press, New York, 1983. 19. Altman, J. C.; Elizando, P. J.; Lipscomb, G. F.; Lytel, R. Mol. Cryst. Liq. Cryst. Inc. Nonlin. Opt. 1988,157,515. RECEIVED
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In Materials for Nonlinear Optics; Marder, S., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1991.
