Abstract
We review our results from spectral studies of the ultrafast excited-state absorption in fullerenes and derivatized fullerenes. These results allow determination of both the spectral response of reverse saturable absorption (RSA) nonlinearities such as optical limiting (OL) in fullerenes, and the dynamical response for different morphologies. We have investigated the effects of thin film and various sol-gel glass environments on the nanosecond OL and femtosecond dynamics of derivatized fullerenes. These data provide evidence of decay pathways which compete with the intersystem crossing to a triplet from the initial singlet states. With appropriate processing, however, the OL response of derivatized-fullerene sol-gel glasses can be enhanced to approach that of the same molecule in solution, while significantly enhancing the optical damage threshold. The optical limiting of these derivatized fullerenes is compared with that of various porphyrin and phthalocyanine molecules.
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L. Tutt and T. Boggess, “A review of optical limiting mechanisms and devices using organics, fullerenes, semiconductors, and other materials,” Prog. Quant. Elect., vol. 17, pp. 299–338, 1993.
L. Tutt and A. Kost, “Optical limiting performance of c60 and c70 solutions,” Nature, vol. 356, pp. 225–226, 1992.
L. Smilowitz, D. McBranch, V. Klimov, J. Robinson, A. Koskelo, M. Grigorova, B. Mattes, H. Wang, and F. Wudl, “Enhanced optical limiting in derivatized fullerenes,” Opt. Lett., vol. 21, p. 922, 1996.
D. McLean, R. Sutherland, M. Brant, D. Brandelik, P. Fleitz, and T. Pottenger, “Nonlinear absorption study of a c60-toluene solution,” Opt. Lett., vol. 18, pp. 858–860, 1993.
R. J. Sension, C. M. Phillips, A. Z. Szarka, W. J. Romanov, A. R. McGhie, J. P. M. Jr A. B. S. III, and R. M. Hochstrasser, “Transient absorption studies of c60 in solution,” J. Phys. Chem., vol. 95, p. 6075, 1991.
T. W. Ebbesen, K. Tanigaki, and S. Kuroshima, “Excited-state properties of c60,” Chem. Phys. Lett. vol. 181, p. 501, 1991.
J. Arbogast, A. Darmanyan, C. Foote, Y. Rubin, F. Diederich, M. Alvarez, S. Anz, and R. Whetten, “Photophysical properties of c60,” J. Phys. Chem., vol. 95, pp. 11–12, 1991.
V. Klimov, D. McBranch, L. Smilowitz, J. Robinson, B. R. Mattes, A. Koskelo, H. Wang, and F. Wudl, “Femtosecond to nanosecond dynamics of c60: implications for excited-state nonlinearities,” Res. Chem. Intermed., special issue, vol. 23, pp. 587–600, 1997.
J. C. Hummelen, B. W. Knight, F. Lepec, F. Wudl, J. Yao, and C. L. Wilkins, “Preparation and characterization of fulleroid and methanofutlerene derivatives,” J. Org. Chem., vol. 60, p. 532, 1995.
D. McBranch, V. Klimov, L. Smilowitz, M. Grigorova, B. R. Mattes, J. Robinson, A. Koskelo, H. Wang, and F. Wudl, “Femtosecond excited-state absorption dynamics and optical limiting in fullerene solutions, sol-gel glasses, and thin films,” SPIE Proceedings, Fullerenes and Photonics III, vol. 2854, p. 140, 1996.
M. Maggini, G. Scorrano, M. Prato, G. Brusatin, P. Innocenzi, M. Guglielmi, A. Renier, R. Signorini, M. Meneghetti, and R. Bozio, “C60 derivatives in sol-gel glasses,” R. Adv. Mater., vol. 7, pp. 404–406, 1995.
R. Kohlman, V. Klimov, M. Grigorova, X. Shi, B. R. Mattes, D. McBranch, H. Wang, F. Wudl, J.-P. Nogués, and W. Moreshead, “Ultrafast and nonlinear optical characterization of optical limiting processes in fullerenes,” SPIE Proceedings, Fullerenes and Photonics IV, p. in press, 1997.
M. Brunel, F. Chaput, S. Vinogradov, C. B, M. Canva, J. P. Boilot, and A. Brun, “Reverse saturable absorption in palladium and zinc tetraphenyltetrabenzoporphyrin doped xerogels,” Chem. Phys., vol. 218, pp. 301–307, 1997.
J. Perry, K. Mansour, I.-Y. Lee, X.-L. Wu, P. Bedworth, C.-T. Chen, D. Ng, S. Marder, P. Miles, T. Wada, M. Tian, and H. Sasabe, “Organic optical limiter with a strong nonlinear absorptive response,” Science, vol. 273, pp. 1533–1536, 1996.
T. Xia, D. J. Hagan, A. Dogariu, A. A. Said, and E. W. V. Stryland, “Optimization of optical limiting devices based on excited-state absorption,” Appl. Opt., vol. 36, no. 18, pp. 4110–4122, 1997.
V. Klimov and D. McBranch, “Femtosecond high-sensitivity, chirp-free transient absorption spectroscopy,” Opt. Lett., submitted.
D. Guldi and K.-D. Asmus, “Photophysical properties of mono- and multiply-functionalized fullerene derivatives,” J. Phys. Chem., vol. 101, pp. 1472–1481, 1997.
S. L. Dexheimer, W. A. Varecka, C. V. Shank, D. Mittelman, and A. Zettl, “Nonexponential relaxation in solid C60 via time-dependent singlet exciton annihilation,” Chem. Phys. Lett., vol. 235, p. 552, 1995.
Acknowledgement
This work was supported in part by LANL Directed Research and Development funds and Collaborative University of California/ Los Alamos Research funds, under the auspices of the U.S. DOE. Additional funding was provided by the U.S. Army Small Business Technology Transfer program, under contract DAAH04-96-C-0077.
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Kohlman, R., Klimov, V., Shi, X. et al. Optical Limiting Processes in Derivatized Fullerenes and Porphyrins/Phthalocyanines. MRS Online Proceedings Library 488, 237–242 (1997). https://doi.org/10.1557/PROC-488-237
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DOI: https://doi.org/10.1557/PROC-488-237