## Nonlinear optical properties of phenoxy-phthalocyanines at 800nm with femtosecond pulse excitation |

Optics Express, Vol. 18, Issue 17, pp. 17666-17671 (2010)

http://dx.doi.org/10.1364/OE.18.017666

Acrobat PDF (783 KB)

### Abstract

We investigated nonlinear optical properties of Phenoxy-phthalocyanine (Pc1) and Phenoxy-phthalocyanine-Zinc(II) (Pc2) at a wavelength of 800 nm with 100 fs pulses .The nonlinear absorption coefficient (*α*) and nonlinear refractive index (*n*_{2}) are measured using standard *Z*-scan technique. Open aperture *Z*-scan indicates strong three-photon absorption in both phthalocyanines. With good solubility and excellent nonlinear optical coefficient,the samples are expected to be a potential candidate for optical applications.

© 2010 OSA

## 1. Introduction

1. D. Kulac, M. Bulut, A. Altındal, A. R. Özkaya, B. Salih, and Ö. Bekaroğlu, “Synthesis and characterization of novel 4-nitro-2-(octyloxy)phenoxy substituted symmetrical and unsymmetrical Zn(II), Co(II) and Lu(III) phthalocyanines,” Polyhedron **26**(18), 5432–5440 (2007). [CrossRef]

2. M. Durmuş and T. Nyokong, “Synthesis, photophysical and photochemical studies of new water-soluble indium(III) phthalocyanines,” Photochem. Photobiol. Sci. **6**(6), 659–668 (2007). [CrossRef] [PubMed]

3. R. S. S. Kumar, S. V. Rao, L. Giribabu, and D. N. Rao, “Femtosecond and nanosecond nonlinear optical properties of alkyl phthalocyanines studied using Z-scan technique,” Chem. Phys. Lett. **447**(4-6), 274–278 (2007). [CrossRef]

4. M. C. Larciprete, R. Ostuni, A. Belardini, M. Alonzo, G. Leahu, E. Fazio, C. Sibilia, and M. Bertolotti, “Nonlinear optical absorption of zinc-phthalocyanines in polymeric matrix,” Photon. Nanostructures **5**(2-3), 73–78 (2007). [CrossRef]

5. H. Isago, K. Miura, and Y. Oyama, “Synthesis and properties of a highly soluble dihydoxo(tetra-tert-butylphthalocyaninato)antimony(V) complex as a precursor toward water-soluble phthalocyanines,” J. Inorg. Biochem. **102**(3), 380–387 (2008). [CrossRef] [PubMed]

## 2. Experiment

*ν*

_{max}/cm

^{−1}: 1230(C-O-C), 3100, 1615, 1530, 1336, 1187, 1130 (Pc skeletal).

^{1}H NMR (DMSO 400MHz):

*δ*, ppm 7.2, 7.31-7.35, 7.5(5H, m, Ph-H), 7.36-7.39, 7.8, 8.1(3H, m, Pc-H)) and Phenoxy-phthalocyanine-Zinc(II) (IR (KBr)

*ν*

_{max}/cm

^{−1}: 1251(C-O-C), 3100, 1608, 1565, 1336, 1180, 1130 (Pc skeletal).

^{1}H NMR (DMSO 400MHz):

*δ*, ppm 7.2, 7.32-7.36, 7.5(5H, m, Ph-H), 7.37-7.41, 7.8, 8.1(3H, m, Pc-H)) were synthesized [6

6. D. K. Modibane and T. Nyokong, “Synthesis and photophysical properties of lead phthalocyanines,” Polyhedron **27**(3), 1102–1110 (2008). [CrossRef]

7. S. B. Mansoor, A. A. Said, T. H. Wei, D. J. Hagan, and E. W. V. Stryland, “Sensitive measurement of optical nonlinearities using a single beam,” IEEE J. Quantum Electron. **26**(4), 760–769 (1990). [CrossRef]

10. Y. Q. Xia, Y. G. Jiang, R. W. Fan, Z. Dong, W. Zhao, D. Chen, and G. Umesh, “Ultrafast nonlinear optical properties of dye-doped PMMA discs irradiated by 40 fs laser pulses,” Opt. Laser Technol. **41**(6), 700–704 (2009). [CrossRef]

^{−4}mol/L.

## 3. Results and discussion

*α*

_{n}is the effective multi-photon absorption coefficient(n = 2 for two-photon absorption; n = 3 for three-photon absorption, and so on),

*I*

_{0}is the intensity of laser beam,

*α*

_{0}the linear absorption coefficient and

*L*is the thickness of the sample,

*z*

_{0}is the diffraction length of the beam.

^{9}W/cm

^{2}. Open circles represent experimental data, the solid line represents theoretical fit with n = 3 (three-photon absorption) and dashed line represents the fit obtained with n = 2(two-photon absorption). The best fit was obtained with the transmission equation for n = 3.

*α*

_{2}(

*α*

_{3}) for Pc1 (Pc2) were obtained with the theoretical fits with Eq. (1) for five different intensities in the range of 4.0 ~11.0 × 10

^{9}W/cm

^{2}.

*α*

_{2}and

*α*

_{3}for the samples are depicted in Fig. 5 . We find that two-photon absorption coefficient (

*α*

_{2}) of samples increases with the energy and three-photon absorption coefficient (

*α*

_{3}) remain constant. Obviously, the nonlinear absorption process involved is certainly three-photon absorption [13

13. F. E. Hernández, K. D. Belfield, and I. Cohanoschi, “Three-photon absorption enhancement in a symmetrical charge transfer fluorene derivative,” Chem. Phys. Lett. **391**(1-3), 22–26 (2004). [CrossRef]

14. T. C. Lin, G. S. He, Q. D. Zheng, and P. N. Prasad, “Degenerate two-/three-photon absorption and optical power-limiting properties in femtosecond regime of a multi-branched chromophore,” J. Mater. Chem. **16**(25), 2490–2498 (2006). [CrossRef]

*α*

_{3}was evaluated from the fits to the experimental data obtained using Eq. (1). The values estimated for Pc1 and Pc2 were 2.84 × 10

^{−18}cm

^{3}/W

^{2}and 7.48 × 10

^{−18}cm

^{3}/W

^{2}, respectively. The nonlinear absorption coefficient of Pc1 (free base) is smaller than the Pc2, which results from the substitution of H

_{2}by metal Zn, the substitution changes the symmetry of the molecular. We have evaluated the three-photon absorption cross-section (

*σ*

_{3}) using the relation

*ω*is the frequency of the laser radiation,

*N*=

*N*is the number of molecules per milliliter,

_{A}C*N*is the Avogadro’s number, and

_{A}*C*is the concentration in mol/L. The values for Pc1 and Pc2 were 0.64 × 10

^{−72}cm

^{6}s

^{2}and 1.69 × 10

^{−72}cm

^{6}s

^{2}, respectively.

^{9}W/cm

^{2}for the two samples, respectively. The close-aperture curve indicates a self-focusing effect and a positive refractive index.

*n*

_{2}) value can be obtained from

*I*

_{0(t)}is the peak intensity at focus and

*S*is the linear transmittance of the aperture given by

*r*

_{a}is the radius of the aperture and

*w*

_{a}is the radius of the laser spot before the aperture. The nonlinear refractive index

*n*

_{2}evaluated using Eq. (2) was 5.7 × 10

^{−15}cm

^{2}/W for the Pc1 and 8.4 × 10

^{−15}cm

^{2}/W for the Pc2 .

*σ*values of 6.1 × 10

_{r}^{−18}cm

^{2}for Pc1 and 3.4 × 10

^{−18}cm

^{2}for Pc2 were obtained. It is obvious that the introduction of Zn, which changes the excited singlet state absorption cross section, also has much influence on the nonlinear refractive index of phthalocyanines [17

17. S. V. Rao, N. Venkatram, L. Giribabu, and D. N. Rao, “Ultrafast nonlinear optical properties of alkyl-phthalocyanine nanoparticles investigated using Z-scan technique,” J. Appl. Phys. **105**(5), 053109 (2009). [CrossRef]

18. L. Howe and J. Z. Zhang, “Ultrafast Studies of Excited-State Dynamics of Phthalocyanine and Zinc Phthalocyanine Tetrasulfonate in Solution,” J. Phys. Chem. A **101**(18), 3207–3213 (1997). [CrossRef]

## 4. Conclusions

^{−18}cm

^{3}/W

^{2}for the free-base phthalocyanine and 16.38 × 10

^{−18}cm

^{3}/W

^{2}for the metallic (Zn) phthalocyanine. The values of the nonlinear refractive indices for Pc1 and Pc2 were estimated to be 0.57 × 10

^{−17}cm

^{2}/W and 0.84 × 10

^{−17}cm

^{2}/W. With good solubility and excellent third order NLO coefficient, the samples are expected to be a potential candidate for optical applications.

## Acknowledgements

## References and Links

1. | D. Kulac, M. Bulut, A. Altındal, A. R. Özkaya, B. Salih, and Ö. Bekaroğlu, “Synthesis and characterization of novel 4-nitro-2-(octyloxy)phenoxy substituted symmetrical and unsymmetrical Zn(II), Co(II) and Lu(III) phthalocyanines,” Polyhedron |

2. | M. Durmuş and T. Nyokong, “Synthesis, photophysical and photochemical studies of new water-soluble indium(III) phthalocyanines,” Photochem. Photobiol. Sci. |

3. | R. S. S. Kumar, S. V. Rao, L. Giribabu, and D. N. Rao, “Femtosecond and nanosecond nonlinear optical properties of alkyl phthalocyanines studied using Z-scan technique,” Chem. Phys. Lett. |

4. | M. C. Larciprete, R. Ostuni, A. Belardini, M. Alonzo, G. Leahu, E. Fazio, C. Sibilia, and M. Bertolotti, “Nonlinear optical absorption of zinc-phthalocyanines in polymeric matrix,” Photon. Nanostructures |

5. | H. Isago, K. Miura, and Y. Oyama, “Synthesis and properties of a highly soluble dihydoxo(tetra-tert-butylphthalocyaninato)antimony(V) complex as a precursor toward water-soluble phthalocyanines,” J. Inorg. Biochem. |

6. | D. K. Modibane and T. Nyokong, “Synthesis and photophysical properties of lead phthalocyanines,” Polyhedron |

7. | S. B. Mansoor, A. A. Said, T. H. Wei, D. J. Hagan, and E. W. V. Stryland, “Sensitive measurement of optical nonlinearities using a single beam,” IEEE J. Quantum Electron. |

8. | M. Samoc, A. Samoc, B. L. Davies, M. G. Humphrey, and M. S. Wong, “Third-order optical nonlinearities of oligomers, dendrimers and polymers derived from solution Z-scan studies,” Opt. Mater. |

9. | G. S. Maciel, A. G. Bezerra-Jr, N. Rakov, C. B. de Araujo, A. S. L. Gomes, and W. M. de Azevedo, “Third-order nonlinear optical properties of undoped polyaniline solutions and films probed at 532 nm,” J. Opt. Soc. Am. B |

10. | Y. Q. Xia, Y. G. Jiang, R. W. Fan, Z. Dong, W. Zhao, D. Chen, and G. Umesh, “Ultrafast nonlinear optical properties of dye-doped PMMA discs irradiated by 40 fs laser pulses,” Opt. Laser Technol. |

11. | 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,” Org. Electron. |

12. | R. L. Sutherland, |

13. | F. E. Hernández, K. D. Belfield, and I. Cohanoschi, “Three-photon absorption enhancement in a symmetrical charge transfer fluorene derivative,” Chem. Phys. Lett. |

14. | T. C. Lin, G. S. He, Q. D. Zheng, and P. N. Prasad, “Degenerate two-/three-photon absorption and optical power-limiting properties in femtosecond regime of a multi-branched chromophore,” J. Mater. Chem. |

15. | C. J. He, Y. Chen, Y. X. Nie, and D. Y. Wang, “Third order optical nonlinearities of eight-β-octa-octyloxy-phthalocyanines,” Opt. Commun. |

16. | G. L. Wood, M. J. Miller, and A. G. Mott, “Investigation of tetrabenzporphyrin by the Z-scan technique,” Opt. Lett. |

17. | S. V. Rao, N. Venkatram, L. Giribabu, and D. N. Rao, “Ultrafast nonlinear optical properties of alkyl-phthalocyanine nanoparticles investigated using Z-scan technique,” J. Appl. Phys. |

18. | L. Howe and J. Z. Zhang, “Ultrafast Studies of Excited-State Dynamics of Phthalocyanine and Zinc Phthalocyanine Tetrasulfonate in Solution,” J. Phys. Chem. A |

**OCIS Codes**

(190.0190) Nonlinear optics : Nonlinear optics

(190.7110) Nonlinear optics : Ultrafast nonlinear optics

**ToC Category:**

Nonlinear Optics

**History**

Original Manuscript: June 9, 2010

Revised Manuscript: July 22, 2010

Manuscript Accepted: July 25, 2010

Published: August 2, 2010

**Citation**

Lei Ma, Yundong Zhang, and Ping Yuan, "Nonlinear optical properties of phenoxy-phthalocyanines at 800nm with femtosecond pulse excitation," Opt. Express **18**, 17666-17671 (2010)

http://www.opticsinfobase.org/oe/abstract.cfm?URI=oe-18-17-17666

Sort: Year | Journal | Reset

### References

- D. Kulac, M. Bulut, A. Altındal, A. R. Özkaya, B. Salih, and Ö. Bekaroğlu, “Synthesis and characterization of novel 4-nitro-2-(octyloxy)phenoxy substituted symmetrical and unsymmetrical Zn(II), Co(II) and Lu(III) phthalocyanines,” Polyhedron 26(18), 5432–5440 (2007). [CrossRef]
- M. Durmuş and T. Nyokong, “Synthesis, photophysical and photochemical studies of new water-soluble indium(III) phthalocyanines,” Photochem. Photobiol. Sci. 6(6), 659–668 (2007). [CrossRef] [PubMed]
- R. S. S. Kumar, S. V. Rao, L. Giribabu, and D. N. Rao, “Femtosecond and nanosecond nonlinear optical properties of alkyl phthalocyanines studied using Z-scan technique,” Chem. Phys. Lett. 447(4-6), 274–278 (2007). [CrossRef]
- M. C. Larciprete, R. Ostuni, A. Belardini, M. Alonzo, G. Leahu, E. Fazio, C. Sibilia, and M. Bertolotti, “Nonlinear optical absorption of zinc-phthalocyanines in polymeric matrix,” Photon. Nanostructures 5(2-3), 73–78 (2007). [CrossRef]
- H. Isago, K. Miura, and Y. Oyama, “Synthesis and properties of a highly soluble dihydoxo(tetra-tert-butylphthalocyaninato)antimony(V) complex as a precursor toward water-soluble phthalocyanines,” J. Inorg. Biochem. 102(3), 380–387 (2008). [CrossRef] [PubMed]
- D. K. Modibane and T. Nyokong, “Synthesis and photophysical properties of lead phthalocyanines,” Polyhedron 27(3), 1102–1110 (2008). [CrossRef]
- S. B. Mansoor, A. A. Said, T. H. Wei, D. J. Hagan, and E. W. V. Stryland, “Sensitive measurement of optical nonlinearities using a single beam,” IEEE J. Quantum Electron. 26(4), 760–769 (1990). [CrossRef]
- M. Samoc, A. Samoc, B. L. Davies, M. G. Humphrey, and M. S. Wong, “Third-order optical nonlinearities of oligomers, dendrimers and polymers derived from solution Z-scan studies,” Opt. Mater. 21(1-3), 485–488 (2003). [CrossRef]
- G. S. Maciel, A. G. Bezerra-Jr, N. Rakov, C. B. de Araujo, A. S. L. Gomes, and W. M. de Azevedo, “Third-order nonlinear optical properties of undoped polyaniline solutions and films probed at 532 nm,” J. Opt. Soc. Am. B 18(8), 1099–1103 (2001). [CrossRef]
- Y. Q. Xia, Y. G. Jiang, R. W. Fan, Z. Dong, W. Zhao, D. Chen, and G. Umesh, “Ultrafast nonlinear optical properties of dye-doped PMMA discs irradiated by 40 fs laser pulses,” Opt. Laser Technol. 41(6), 700–704 (2009). [CrossRef]
- 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,” Org. Electron. 8(2-3), 198–205 (2007). [CrossRef]
- R. L. Sutherland, Handbook of Nonlinear Optics. Second Edition (Marcel Dekker, Inc. New York, 2003), Chap. 9.
- F. E. Hernández, K. D. Belfield, and I. Cohanoschi, “Three-photon absorption enhancement in a symmetrical charge transfer fluorene derivative,” Chem. Phys. Lett. 391(1-3), 22–26 (2004). [CrossRef]
- T. C. Lin, G. S. He, Q. D. Zheng, and P. N. Prasad, “Degenerate two-/three-photon absorption and optical power-limiting properties in femtosecond regime of a multi-branched chromophore,” J. Mater. Chem. 16(25), 2490–2498 (2006). [CrossRef]
- C. J. He, Y. Chen, Y. X. Nie, and D. Y. Wang, “Third order optical nonlinearities of eight-β-octa-octyloxy-phthalocyanines,” Opt. Commun. 271(1), 253–256 (2007). [CrossRef]
- G. L. Wood, M. J. Miller, and A. G. Mott, “Investigation of tetrabenzporphyrin by the Z-scan technique,” Opt. Lett. 20(9), 973–975 (1995). [CrossRef] [PubMed]
- S. V. Rao, N. Venkatram, L. Giribabu, and D. N. Rao, “Ultrafast nonlinear optical properties of alkyl-phthalocyanine nanoparticles investigated using Z-scan technique,” J. Appl. Phys. 105(5), 053109 (2009). [CrossRef]
- L. Howe and J. Z. Zhang, “Ultrafast Studies of Excited-State Dynamics of Phthalocyanine and Zinc Phthalocyanine Tetrasulfonate in Solution,” J. Phys. Chem. A 101(18), 3207–3213 (1997). [CrossRef]

## Cited By |
Alert me when this paper is cited |

OSA is able to provide readers links to articles that cite this paper by participating in CrossRef's Cited-By Linking service. CrossRef includes content from more than 3000 publishers and societies. In addition to listing OSA journal articles that cite this paper, citing articles from other participating publishers will also be listed.

« Previous Article | Next Article »

OSA is a member of CrossRef.