We have investigated the nonlinear optical properties, optical limiting thresholds, and figures of merits for five different phthalocyanine thin films, achieved through doping in PMMA polymer, using the Z-scan technique at 800 nm with 2 ps laser pulse excitation. From the open-aperture Z-scan data we derived that these molecules exhibit strong two photon absorption (2PA) with the nonlinear coefficients in the range of 15 - 200 cm/GW. We have also estimated the sign and magnitude of real part of third order nonlinearity through the closed aperture data. Preliminary femtosecond pump-probe data suggests that the lifetimes of excited states are in the sub-100 ps regime for all the molecules in film form. Our studies provide concrete evidence that these phthalocyanines are prospective candidates for multi-photon imaging and optical limiting applications.
KeywordsZ-ScanPhthalocyaninesThin FilmsPicosecondFigures of Merit
P. N. Prasad and D. R. Ulrich, “Nonlinear Optical and Electro-active Polymers,” Plenum Press, New York, 1998.
J. L. Bredas and R. R. Chance, “Conjugated Polymeric Materials: Opportunities in Electronics, Optoelectronics and Molecular Electronics,” Kluwer Academic, Dordrecht, 1990.
W. Denk, J. H. Strickler and W. W. Webb, “Two-Photon Laser Scanning Fluorescence Microscopy,” Science, Vol. 248, No. 4951, April 1990, pp. 73-76. doi:10.1126/science.2321027
D. A. Parthenopoulos, P. M. Rentzepis, ““3-Dimensional Optical Storage Memory,” Science, Vol. 245, No. 4920, 1989, pp. 843-845. doi:10.1126/science.245.4920.843
G. S. He, L.-S. Tan, Q. Zheng and P. N. Prasad, “Multi-Photon Absorbing Materials: Molecular Designs, Syntheses, Characterizations, and Applications,” Chemical Reviews, Vol. 108, No. 4, April 2008, pp. 1245-1330. doi:10.1021/cr050054x
A. S. Dvornikov, E. P. Walker, and P. M. Rentzepis, “Two-Photon Three-Dimensional Optical Storage Memory,” The Journal of Physical Chemistry A, Vol. 113, No. 49, December 2009, pp. 13633-13644. doi:10.1021/jp905655z
K. D. Belfield, K. J. Schafer, Y. Liu, J. Liu, X. Ren and E. W. van Stryland, “Mul-tiphoton-Absorbing Organic Materials for Microfabrication, Emerging Optical Applications and Non-Destructive Three-Dimensional Imaging,” Journal of Physical Organic Chemistry, Vol. 13, No. 12, December 2000, pp. 837-849.
S. V. Rao, N. K. M. N. Srinivas, L. Giribabu, B. G. Maiya, D. N. Rao, R. Philip and G. R. Kumar, “Studies of Third-Order Optical Nonlinearity and Nonlinear Absorption in Tetratolyl Porphyrins Using Degenerate Four Wave Mixing and Z-Scan,” Optics Communications, Vol. 182, No. 1-3, August 2000, pp. 255-264. doi:10.1016/S0030-4018(00)00808-7
N. K. M. N. Srinivas, S. V. Rao, and D. N. Rao, “Wavelength Dependent Studies of Nonlinear Absorption in Znmp TBP Using Z-Scan,” Journal of Porphyrins and Phthalocyanines, Vol. 5, No. 7, May 2001, pp. 549-554. doi:10.1002/jpp.357
B. K. Mandal, B. Bihari, A. K. Sinha and M. Kamath, “Third-Order Nonlinear Optical Response in a Multilayered Phthalocyanine Composite,” Applied Physics Letters, Vol. 66, No. 8, January 1995, pp. 932-934. doi:10.1063/1.113601
C. Y. He, Y. Q. Wu, G. Shi, W. B. Duan, W. Song and Y. L. Song, “Large Third-Order Optical Nonlinearities of Ultrathin Films Containing Octacarboxylic Copper Phthalocyanine,” Organic Electronics, Vol. 8, No. 2-3, April-June 2007, pp. 198-205. doi:10.1016/j.orgel.2007.01.002
L. Guo, G. Ma, Y. Liu, J. Mi, S. Qian and L. Qiu, “Optical and Non-Linear Optical Properties of Vanadium Oxide Phthalocyanine Films,” Applied Physics B, Vol. 74, No. 3, March 2002, pp. 253-257. doi:10.1007/s003400200801
G. Ma, L. Guo, J. Mi, Y. Liu, D. Pan and Y. Huang, “Femtosecond Nonlinear Optical Response of metallophthalocyanine Films,” Solid State Communications, Vol. 118, No. 12, June 2001, pp. 633-638. doi:10.1016/S0038-1098(01)00183-1
M. Q. Tian, S. Yangi, K. Sasaki and H. Sasabe, “Syntheses and Nonlinear Optical Properties of Nonaggregated Metallophthalocyanines,” Journal of the Optical Society of America B: Optical Physics, Vol. 15, No. 2, February 1998, pp. 846-853. doi:10.1364/JOSAB.15.000846
L. Ma, Y. Zhang and P. Yuan, “Nonlinear Optical Properties of Phenoxy-Phthalocyanines at 800 nm with Femtosecond Pulse Excitation,” Optics Express, Vol. 18, No. 17, August 2010, pp. 17666-17671. doi:10.1364/OE.18.017666
G. Ma, L. Guo, J. Mi, Y. Liu, S. Qian, D. Pan and Y. Huang, “Ultrafast Optical Nonlinearity of Titanylphthalocyanine Films,” Thin Solid Films, Vol. 410, No. 1-2, May 2002, pp. 205-211. doi:10.1016/S0040-6090(02)00246-8
H. S. Nalwa, A. Kakuta, “Third-Order Non-Linear Optical Properties of Donor- and Acceptor-Substituted Metallophthalocyanines,” Thin Solid Films, Vol. 254, No. 1-2, January, 1995, pp. 218-223. doi:10.1016/0040-6090(94)06260-R
T.-H. Tran-Thi, T. Fournier, A. Y. Sharanov, N. Tka- chenko, H. Lemmetyinen, P. Grenier, K.-D. Truong and D. Houde, “Photophysical, Photoelectrical and Non-Linear Optical Properties of Porphyrin-Phthalocyanine Assemblies in Langmuir-Blodgett Films,” Thin Solid Films, Vol. 273, No. 1-2, January 1996, pp. 8-13. doi:10.1016/0040-6090(95)06763-9
S. Fang, H. Hoshi, K. Kohama and Y. Maruyama, “Nonlinear Optical Characteristics of Vanadyl Phthalocyanine Thin Film Grown by the Molecular Beam Epitaxial Method,” Journal of Physical Chemistry, Vol. 100, No. 10, March 1996, pp. 4104-4110. doi:10.1021/jp953093t
C. He, W. Duan, G. Shi, Y. Wu, Q. Ouyang and Y. Song, “Strong Nonlinear Optical Refractive Effect of Self-Assembled Multilayer Films Containing Tetrasulfonated Iron Phthalocyanine,” Applied Surface Science, Vol. 255, No. 8, February 2009, pp. 4696-4701. doi:10.1016/j.apsusc.2008.11.088
Y. Sakai, M Ueda, A. Yahagi and N. Tanno, “Synthesis and Properties of Aluminum Phthalocyanine Side-Chain Polyimide for Third-Order Nonlinear Optics,” Polymer, Vol. 43, No. 12, June 2002, pp. 3497-3503. doi:10.1016/S0032-3861(02)00021-6
M. Yamashita, F. Inui, K. Irokawa, A. Morinaga, T. Tako, A. Mito and H. Moriwaki, “Nonlinear Optical Properties of Tin-Phthalocyanine Thin Films,” Applied Surface Science, Vol. 130-132, June 1998, pp. 883-888. doi:10.1016/S0169-4332(98)00170-6
G. Fu, T. Yoda, K. Kasatani, H. Okamoto and S. Takenaka, “Third-Order Optical Nonlinearities of Naphthalocyanine-Derivative-Doped Polymer Films Measured by Resonant Femtosecond Degenerate Four-Wave Mixing,” Japanese Journal of Applied Physics, Vol. 44, No. 6A, June 2005, pp. 3945-3950. doi:10.1143/JJAP.44.3945
S. Fang, H. Tada and S. Mashiko, “Enhancement of the Third-Order Nonlinear Optical Susceptibility in Epitaxial Vanadyl-Phthalocyanine Films Grown on KBr,” Applied Physics Letters, Vol. 69, No.6, February 1996, pp. 767- 769. doi:10.1063/1.117885
S. J. Mathews, S. C. Kumar, L. Giribabu and S. V. Rao, “Nonlinear Optical and Optical Limiting Properties of Phthalocyanines in Solution and Thin Films of PMMA Studied Using a Low Power He-Ne Laser,” Materials Letters, Vol. 61, No. 22, September 2007, pp. 4426-4431. doi:10.1016/j.matlet.2007.02.034
S. J. Mathews, S. C. Kumar, L. Giribabu and S. V. Rao, “Large Third Order Nonlinear Optical and Optical Limiting Properties of Symmetric and Unsymmetrical Phthalocyanines Studied Using Z-Scan,” Optics Communications, Vol. 280, No. 1, December 2007, pp. 206-212. doi:10.1016/j.optcom.2007.08.022
N. Venkatram, L. Giribabu, D. N. Rao and S. V. Rao, “Nonlinear Optical and Optical Limiting Studies in Alkoxy Phthalocyanines Studied at 532 nm with Nanosecond Pulse Excitation”, Applied Physics B: Lasers and Optics, Vol. 91, No. 1, April 2008, pp. 149-156. doi:10.1007/s00340-008-2934-5
N. Venkatram, L. Giribabu, D. N. Rao and S. V. Rao, “Femtosecond Nonlinear Optical Properties of Alkoxy Phthalocyanines at 800 nm Studied with Z-Scan Technique,” Chemical Physics Letters, Vol. 464, No. 4-6, October 2008, pp. 211-215. doi:10.1016/j.cplett.2008.09.029
R. S. S. Kumar, S. V. Rao, L. Giribabu and D. N. Rao, “Femtosecond and Nanosecond Nonlinear Optical Properties of Alkly Phthalocyanines Studied Using Z-Scan,” Chemical Physics Letters, Vol. 447, No. 4-6, October 2007, pp. 274-278. doi:10.1016/j.cplett.2007.09.028
R. S. S. Kumar, S. V. Rao, L. Giribabu and D. N. Rao, “Ultrafast Nonlinear Optical Properties of Alkyl Phthalocyanines Investigated Using Degenerate Four-Wave Mixing Technique,” Optical Materials, Vol. 31, No. 6, April 2009, pp. 1042-1047. doi:10.1016/j.optmat.2008.11.018
P. T. Anusha, P. S. Reeta, L. Giribabu, S. P. Tewari and S. V. Rao, “Picosecond Optical Nonlinearities of Unsymmetrical Alkyl and Alkoxy Phthalocyanines Studied Using the Z-Scan Technique,” Materials Letters, Vol. 64, No. 17, September 2010, pp. 1915-197. doi:10.1016/j.matlet.2010.06.004
S. V. Rao, P. T. Anusha, L. Giribabu and S. P. Tewari, “Picosecond Optical Nonlinearities in Symmetrical and Unsymmetrical Phthalocyanines Studied Using the Z-Scan Technique,” PRAMANA-Journal of Physics, Vol. 75, No.5, November 2010, pp. 1017-1023.
S. V. Rao, N. Venkatram, L. Giribabu and D. N. Rao, “Ultrafast Nonlinear Optical Properties of Phthalocyanines Nanoparticles at 800 nm Studied Using Z-Scan,” Journal of Applied Physics, Vol. 105, No. 5, March 2009, pp. 053109-053109-6. doi:10.1063/1.3079801
A. Gadalla, J.-B. Beaufrand, M. Bowen, S. Boukari, E. Beaurepaire, O. Cregut, M. Gallart, B. Honerlage and P. Gilliot, “Ultrafast Optical Dynamics of Metal-Free and Cobalt Phthalocyanine Thin Films II: Study of Excited-State Dynamics,” The Journal of Physical Chemistry C, Vol. 114, No. 41, September 2010, pp. 17854- 17863. doi:10.1021/jp104875u
A. Gadalla, O. Cregut, M. Gallart, B. Honerlage, J.-B. Beaufrand, M. Bowen, S. Boukari, E. Beaurepaire and P. Gilliot, “Ultrafast Optical Dynamics of Metal-Free and Cobalt Phthalocyanine Thin Films,” The Journal of Physical Chemistry C, Vol. 114, No. 9, February 2010, pp. 4086-4092. doi:10.1021/jp911438y
M. S. Bahae, A. A. Said, T. H. Wei, D. J. Hagan and E. W. van Stryland, “Sensitive Measurements of Optical Nonlinearities Using a Single Beam,” IEEE Journal of Quantum Electronics, Vol. 26, No. 4, April 1990, pp. 760-769. doi:10.1109/3.53394
N. K. M. N. Srinivas, S. V. Rao and D. N. Rao, “Saturable and Reverse Saturable Absorption Properties of Rhodamine B in Methanol and Water,” Journal of the Optical Society of America B, Vol. 20, No. 12, December 2003, pp. 2470-2479. doi:10.1364/JOSAB.20.002470
B. Gu, X. Q. Huang, S. Q. Tan, M. Wang and W. Ji, “Z-Scan Analytical Theories for Characterizing Multiphoton Absorbers,” Applied Physics B: Lasers and Optics, Vol. 95, No. 2, May 2009, pp. 375-381. doi:10.1007/s00340-009-3426-y
B. Gu, J. Wang, J. Chen, Y.-X. Fan, J. Ding and H.-T. Wang, “Z-Scan Theory for Material with Two- and Three-Photon Absorption,” Optics Express, Vol. 13, No. 23, 2005, pp. 9230-9234. doi:10.1364/OPEX.13.009230
B. Gu, W. Ji, H. Z. Yang and H. T. Wang, “Theoretical and Experimental Studies of Three-Photon-Induced Excited-State Absorption,” Applied Physics Letters, Vol. 96, No. 8, February 2010, pp. 081104 (3 pages).
B. Gu, K. Lou, J. Chen, H.-T. Wang and W. Ji, “Determination of the Nonlinear Refractive Index in Multiphoton Absorbers by Z-Scan Measurements,” Journal of the Optical Society of America B, Vol. 27, No. 11, November 2010, pp. 2438-2442.
S. V. Rao, D. Swain and S. P. Tewari, “Pump-Probe Experiments with sub-100 Femtosecond Pulses for Characterizing the Excited State Dynamics of Phthalocyanine thin Film,” In: R. L. Nelson, F. Kajzar and T. Kaino, Eds., Organic Photonic Materials and Devices XII, Proceedings of the SPIE, Vol. 7599, March 2010, pp. 75991P1-75991P8.
L. Howe and J. Z. Zhang, “Ultrafast Studies of Excited-State Dynamics of Phthalocyanine and Zinc Phthalo- cyanine Tetrasulfonate in Solution,” The Journal of Physical Chemistry A, Vol. 101, No. 18, May 1997, pp. 3207-3213. doi:10.1021/jp9622445
T. Asahi, N. Tamai, T. Uchida, N. Shimo and H. Masuhara, “Nonlinear Excited-State Dynamics of a Thin Copper Phthalocyanine Film by Femtosecond Transient Grating Spectroscopy,” Chemical Physics Letters, Vol. 234, No. 4-6, March 1995, pp. 337-342. doi:10.1016/0009-2614(95)00047-8
E. Tokunaga1, A. Terasaki, V. S. Valencia, T. Wada, H. Sasabe and T. Kobayashi, “Femtosecond Phase Spectroscopy of Multi-Level Systems: Phthalocyanines,” Applied Physics B: Lasers and Optics, Vol. 63, No. 3, September 1996, pp. 255-264.
M. Fournier, C. Pépin, D. Houde, R. Ouellet and J. E. van Lier, “Ultrafast Studies of the Excited-State Dynamics of Copper and Nickel Phthalocyanine Tetrasulfonates: Potential Sensitizers for Two-Photon Photodynamic Therapy of Tumors,” Photochemical & Photobiological Sciences, Vol. 3, No. 1, January 2004, pp. 120-126. doi:10.1039/b302787b