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Optics Express

Optics Express

  • Editor: C. Martijn de Sterke
  • Vol. 15, Iss. 11 — May. 28, 2007
  • pp: 6868–6873
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Photo-responsive properties and heating-induced surface relief patterns from azobenzene-doped GeO2/γ-glycidoxypropyltrimethoxysilane organic-inorganic hybrid films

Wenxiu Que, Z. Sun, L. L. Wang, and T. Chen  »View Author Affiliations


Optics Express, Vol. 15, Issue 11, pp. 6868-6873 (2007)
http://dx.doi.org/10.1364/OE.15.006868


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Abstract

GeO2/γ-glycidoxypropyltrimethoxysilane organic-inorganic hybrid optical waveguide films, which contain azobenzene small molecular groups, have been prepared by combining a low temperature sol-gel process with a spin-coating technique. The azobenzene in hybrid films can undergo trans-cis-trans photoisomerization efficiently by a photoirradiation with UV light. It is also found interestingly that surface relief patterns can be heat-induced on such azobenzene-containing small molecular hybrid films, but can be erased by further heating the hybrid film and no permanent damage of the hybrid film is observed. The refractive index, thickness, and morphologic properties of the hybrid films have also been investigated by a prism coupling technique and atomic force microscopy. These results indicate that the azodye-doped hybrid films are promising candidates for integrated optics and photonic applications, which allow directly integrating on the same chip waveguide device with the optical data storage and optical switching devices.

© 2007 Optical Society of America

1. Introduction

As one knows well now, the trans-cis-trans photoisomerization process results in the reorientation of azodye molecules, which is promising and potential applications in various photonic devices, such as optical storage, optical switch, and nonlinear optics applications. Therefore, polymers containing azobenzene chromophore molecules or azobenzene-based photochromic polymers have been studied extensively by many research groups due to their promising photonic applications over the past ten years. [1–3

1. X. L. Jiang, L Li, J. Kumar, D. Y. Kim, V. Shivshankar, and S. K. Tripathy, “Polarization dependent recordings of surface relief gratings on azobenzene containing polymer films,” Appl. Phys. Lett. 19, 2618–2620 (1996). [CrossRef]

]. Considering that most photoactive organic materials may not be stable in ambient environment for long periods of time, low-mechanical strength, and relative low optical transparency as compared to that of an inorganic oxide. Recently, optically homogeneous and transparent organic-inorganic hybrids containing organic components have been widely studied and indicated that the optical properties of them can be largely enhanced as compared with organic polymer materials [4–6

4. F. Chaput, J. P. Boilot, D. Riehl, and Y. Lévy, “Modified sol-gel films for optical storage,” J. Sol-Gel Sci. & Technol. 2, 779–782 (1994). [CrossRef]

]. The introduction of organic groups into an inorganic network improves mechanical properties, leading to the easier processing of thick film and the modification of an inorganic network structure with organic groups gives larger space for the isomerization of organic photoactive molecules as compared to inorganic glasses [7

7. D. Levy, S. Einhorn, and D. Avnir, “Applications of the sol-gel process for the preparation of photochromic information-recording materials: synthesis, properties, mechanisms,” J. Non-cryst. Solids 113, 137 (1989). [CrossRef]

]. Therefore, organic-inorganic hybrids are thus anticipated as desirable materials for photonic applications, which can trap organic molecules. Especially, organic-inorganic hybrid waveguide film configuration become more important, they can be obtained at a low heat treatment temperature, which would allow directly integrating on the same chip waveguide device with other optoelectronic components. Therefore, including TiO2/ormosil and ZrO2/ormosil hybrid materials have been reported and studied by the sol-gel technique [8–10

8. P. Innocenzi, G. Battaglin, M. Guglielmi, R. Signorini, R. Bozio, and M. Maggini, “3-(Glycidoxypropyl)-trimethoxysilane-TiO2 hybrid organic-inorganic materials for optical limiting,” J. Non-Cryst. Solids 265, 68–74 (2000). [CrossRef]

]. However, the germanosilicate glasses, which have high optical transmission in the visible and infrared range, as core dopant and silica as the substrate ensure that these waveguides will have virtually identical characteristics to single-mode fibers, indicating they are potentially ideal applications for integrated photonics devices.

2. Experimental Study

The thickness and the refractive index of the hybrid films were measured for transverse electric (TE) polarization by an m-line apparatus (Metricon 2010) based on the prism coupling technique at the wavelengths of 633. The photo-responsive measurements of the hybrid films were carried out by a Shimadzu UV-2501 PC UV-Vis spectrophotometer after irradiated by UV light for various time intervals. The UV irradiation light was produced by a Driel Instrument 66901 500 Watts mercury lamp through a filter centered at 362 nm with a circular cooling water system to maintain the lamp temperature at about 5°C. The UV irradiation light intensity was 2.0mW/cm2. The surface relief patterns, which were induced by heating at a certain temperature, of the hybrid films were observed by a Digital Instruments Nanoscope IIIa AFM using the tapping mode.

3. Results and discussion

It was shown that dense and highly transparent azobenzene-containing small molecular GeO2/GLYMO organic-inorganic hybrid waveguide films could be obtained below a low heat treatment temperature of 150°C. Light wave guiding was easily demonstrated when such a film was deposited on a silica-on-silicon substrate. Our experimental results also indicate that a crack-free hybrid film with a thickness of more than 10 μm could be obtained by a multiple spin-coating process and heated at 100°C.

The thickness and refractive index of the hybrid films heated at different heat treatment temperatures were also estimated. As expected, with increase the heat treatment temperature, the refractive index of the hybrid film increases and the thickness drops. That is to say, the film thickness becomes thinner and the refractive index becomes higher as the heat treatment temperature rises. For example, the thickness and refractive index for the hybrid film obtained at room temperature are 1.67 μm and 1.496, but for the hybrid film heated at 100°C, they are 1.62 μm and 1.499, respectively. It should be mentioned here that the thickness and refractive index of the hybrid film are not sensitive to the heat treatment temperature in the range between room temperature and 150°C. For example, the decrease of the film thickness is about 4.3 % and the increase of the refractive index is about 0.3%, respectively, when the heat treatment temperature is increased from room temperature to 150°C. However, the change in the film thickness and refractive index is more substantial when the heat treatment temperature is further increased from 150°C up to 200°C. It can be also obtained that within the heat treatment temperature range between room temperature and 200°C, the refractive index of the hybrid film can be varied from 1.496 to 1.505 at the wavelength of 633 nm.

Fig. 1. UV-Vis absorbance changes of the hybrid film upon irradiation at UV of 362 nm and light intensity of 2 mW/cm2. (a) Film obtained at room temperature, (b) Film heated at 120°C

Fig. 2. AFM image of the surface relief patterns formed on azobenzene-containing hybrid film heated at 80°C
Fig. 3. AFM image of the surface relief patterns formed on azobenzene-containing hybrid film heated at 120°C

4. Conclusions

In conclusion, a new azobenzene-containing GeO2/GLYMO hybrid material for photonic applications has been prepared by the sol-gel process from an organic-inorganic hybrid system. The hybrid films have showed photoresponsive properties of the trans-cis-trans photoisomerization by the irradiation of UV to verify its optical storage and switching characteristics. We have demonstrated that such a hybrid film can be used for surface relief structure induced by heating and the surface relief structure has can keep good stability. Note that the as prepared hybrid films used to form the surface relief patterns shown in Fig. 3 is the first example of such structure formation in such a low temperature organic-inorganic hybrid material induced by a certain heat treatment temperature. The results show that azobenzene has been incorporated into silicon oxide matrices by the sol-gel technique. In addition, the planar waveguide properties of the hybrid films doped with azodyes and heated at different temperatures have been investigated. The present study shows that the hybrid materials are promising candidates for materials photonic applications.

Acknowledgment

This work was supported by the National Natural Science Foundation of China under Grant No. 60477003.

References and links

1.

X. L. Jiang, L Li, J. Kumar, D. Y. Kim, V. Shivshankar, and S. K. Tripathy, “Polarization dependent recordings of surface relief gratings on azobenzene containing polymer films,” Appl. Phys. Lett. 19, 2618–2620 (1996). [CrossRef]

2.

A. Sharma, M. Dokhanian, and A. Kassu, “Photoinduced grating formation in azo-dye-labeled phospholipids thin films by 244-nm light,” Opt. Lett 30, 501–503 (2005). [CrossRef] [PubMed]

3.

M. Z. Alam, T. Ohmachi, T. Ogata, T. Nonaka, and S. Kurihara, “Photoisomerization behavior and photoinduced surface relief gratings on azopolymer film by a monochromatic light irradiation,” Opt. Mater. 29, 365–370 (2006). [CrossRef]

4.

F. Chaput, J. P. Boilot, D. Riehl, and Y. Lévy, “Modified sol-gel films for optical storage,” J. Sol-Gel Sci. & Technol. 2, 779–782 (1994). [CrossRef]

5.

B. Lebeau, C. Sanchez, S. Brasselet, J. Zyss, G. Froc, and M. Dumont, “Large second-order optical nonlinearities in azo dyes grafted hybrid sol-gel coatings,” New J. Chem. 20, 13–18 (1996).

6.

J. A. Gurney, I. Vargas-Baca, A. P. Brown, M. P. Andrews, and S. I. Najafi, “Azo-dye hybrid sol-sel glass composites for optoelectronics,” Proc. SPIE 3469, 145–152 (1998). [CrossRef]

7.

D. Levy, S. Einhorn, and D. Avnir, “Applications of the sol-gel process for the preparation of photochromic information-recording materials: synthesis, properties, mechanisms,” J. Non-cryst. Solids 113, 137 (1989). [CrossRef]

8.

P. Innocenzi, G. Battaglin, M. Guglielmi, R. Signorini, R. Bozio, and M. Maggini, “3-(Glycidoxypropyl)-trimethoxysilane-TiO2 hybrid organic-inorganic materials for optical limiting,” J. Non-Cryst. Solids 265, 68–74 (2000). [CrossRef]

9.

S. J. L. Ribeiro, Y. Messaddeq, R. R. Goncalves, M. Ferrari, M. Montagna, and M. A. Aegerter, “Low optical loss planar waveguides prepared in organic-inorganic hybrid system,” Appl. Phys. Lett. 77, 3502–3504 (2000). [CrossRef]

10.

W. X. Que, Y. Zhou, Y. L. Lam, Y. C. Chan, and C. H. Kam, “Optical and microstructural properties of sol-gel derived titania/organically modified silane thin films,” Thin Solid Films 358, 16–21 (2000). [CrossRef]

11.

W. X. Que, X. Hu, and Q. Y. Zhang, “Germania/ormosil hybrid materials derived at low temperature for photonic applications,” Appl. Phys. B 76, 423–427 (2003). [CrossRef]

12.

W. X. Que, L. L. Wang, T. Chen, Z. Sun, and X. Hu, “Preparation and spectroscopic studies of sol-gel derived GeO2/organically modified silane hybrid materials for optical waveguides,” J. Sol-Gel Sci. Techn. 38, 147–152 (2006). [CrossRef]

13.

J. D. Y. Kim, S. K. Tripathy, L. Li, and J. Kumar, “Laser-induced holographic surface relief gratings on nonlinear optical polymer films,” Appl. Phys. Lett. 66, 1166–1168 (1995). [CrossRef]

14.

T. Ubukata, T. Seki, and K. Ichimura, “Surface relief gratings in host-guest supramolecular materials,” Adv. Mater. 12, 1675–1678 (2000). [CrossRef]

15.

J. Guo, Y. N. He, H. P. Xu, B. Song, X. Zhang, Z. Q. Wang, and X. G. Wang, “Azobenzene-containing supramolecular polymer films for laser-induced surface relief gratings,” Chem. Mater. 19, 14–17 (2007). [CrossRef]

OCIS Codes
(210.4810) Optical data storage : Optical storage-recording materials
(260.5130) Physical optics : Photochemistry
(310.6860) Thin films : Thin films, optical properties

ToC Category:
Optical Data Storage

History
Original Manuscript: April 2, 2007
Revised Manuscript: May 2, 2007
Manuscript Accepted: May 2, 2007
Published: May 18, 2007

Citation
Wenxiu Que, Z. Sun, L. L. Wang, and T. Chen, "Photo-responsive properties and heating-induced surface relief patterns from azobenzene-doped GeO2/γ-glycidoxypropyltrimethoxysilane organic-inorganic hybrid films," Opt. Express 15, 6868-6873 (2007)
http://www.opticsinfobase.org/oe/abstract.cfm?URI=oe-15-11-6868


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References

  1. X. L. Jiang, L Li, J. Kumar, D. Y. Kim, V. Shivshankar, and S. K. Tripathy, "Polarization dependent recordings of surface relief gratings on azobenzene containing polymer films," Appl. Phys. Lett. 19, 2618-2620 (1996). [CrossRef]
  2. A. Sharma, M. Dokhanian, and A. Kassu, "Photoinduced grating formation in azo-dye-labeled phospholipids thin films by 244-nm light," Opt. Lett 30, 501-503 (2005). [CrossRef] [PubMed]
  3. M. Z. Alam, T. Ohmachi, T. Ogata, T. Nonaka, and S. Kurihara, "Photoisomerization behavior and photoinduced surface relief gratings on azopolymer film by a monochromatic light irradiation," Opt. Mater. 29, 365-370 (2006). [CrossRef]
  4. F. Chaput, J. P. Boilot, D. Riehl, and Y. Lévy, "Modified sol-gel films for optical storage," J. Sol-Gel Sci. &Technol. 2, 779-782 (1994). [CrossRef]
  5. B. Lebeau, C. Sanchez, S. Brasselet, J. Zyss, G. Froc, and M. Dumont, "Large second-order optical nonlinearities in azo dyes grafted hybrid sol-gel coatings," New J. Chem. 20, 13-18 (1996).
  6. J. A. Gurney, I. Vargas-Baca, A. P. Brown, M. P. Andrews, and S. I. Najafi, "Azo-dye hybrid sol-sel glass composites for optoelectronics," Proc. SPIE 3469, 145-152 (1998). [CrossRef]
  7. D. Levy, S. Einhorn, and D. Avnir, "Applications of the sol-gel process for the preparation of photochromic information-recording materials: synthesis, properties, mechanisms," J. Non-cryst. Solids 113, 137 (1989). [CrossRef]
  8. P. Innocenzi, G. Battaglin, M. Guglielmi, R. Signorini, R. Bozio, and M. Maggini, "3-(Glycidoxypropyl)-trimethoxysilane-TiO2 hybrid organic-inorganic materials for optical limiting," J. Non-Cryst. Solids 265, 68-74 (2000). [CrossRef]
  9. S. J. L. Ribeiro, Y. Messaddeq, R. R. Goncalves, M. Ferrari, M. Montagna, and M. A. Aegerter, "Low optical loss planar waveguides prepared in organic-inorganic hybrid system," Appl. Phys. Lett. 77, 3502-3504 (2000). [CrossRef]
  10. W. X. Que, Y. Zhou, Y. L. Lam, Y. C. Chan, and C. H. Kam, "Optical and microstructural properties of sol-gel derived titania/organically modified silane thin films," Thin Solid Films 358, 16-21 (2000). [CrossRef]
  11. W. X. Que, X. Hu, and Q. Y. Zhang, "Germania/ormosil hybrid materials derived at low temperature for photonic applications," Appl. Phys. B 76, 423-427 (2003). [CrossRef]
  12. W. X. Que, L. L. Wang, T. Chen, Z. Sun, X. Hu, "Preparation and spectroscopic studies of sol-gel derived GeO2/organically modified silane hybrid materials for optical waveguides," J. Sol-Gel Sci. Technol. 38, 147-152 (2006). [CrossRef]
  13. J D. Y. Kim, S. K. Tripathy, L. Li, and J. Kumar, "Laser-induced holographic surface relief gratings on nonlinear optical polymer films," Appl. Phys. Lett. 66, 1166-1168 (1995). [CrossRef]
  14. T. Ubukata, T. Seki, and K. Ichimura, "Surface relief gratings in host-guest supramolecular materials," Adv. Mater. 12, 1675-1678 (2000). [CrossRef]
  15. J. Guo, Y. N. He, H. P. Xu, B. Song, X. Zhang, Z. Q. Wang, and X. G. Wang, "Azobenzene-containing supramolecular polymer films for laser-induced surface relief gratings," Chem. Mater. 19, 14-17 (2007). [CrossRef]

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