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Virtual Journal for Biomedical Optics

Virtual Journal for Biomedical Optics

| EXPLORING THE INTERFACE OF LIGHT AND BIOMEDICINE

  • Editor: Gregory W. Faris
  • Vol. 4, Iss. 2 — Feb. 10, 2009
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Large enhancement of femtosecond laser micromachining speed in dye-doped hydrogel polymers

Li Ding, Dharmendra Jani, Jeffrey Linhardt, Jay F. Künzler, Siddhesh Pawar, Glen Labenski, Thomas Smith, and Wayne H. Knox  »View Author Affiliations


Optics Express, Vol. 16, Issue 26, pp. 21914-21921 (2008)
http://dx.doi.org/10.1364/OE.16.021914


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Abstract

Ophthalmologic hydrogel polymers are doped with Fluorescein or Coumarin dyes prior to the femtosecond laser micromachining process. We find that the achievable micromachining writing speed can be greatly increased while maintaining large refractive index changes (up to +0.08). Compared with previous results in dye-doped polymers that do not contain water such as PMMA, we obtain much larger index changes and much faster writing speeds.

© 2008 Optical Society of America

1. Introduction

Near infrared femtosecond laser micromachining has been demonstrated to be a powerful microfabrication tool, attracting increasing interest in the fields of optics, semiconductors, biomedicine and microelectronics [1

1. K. M. Davis, K. Miura, N. Sugimoto, and K. Hirao, “Writing waveguides in glass with a femtosecond laser,” Opt. Lett. 21, 1729–1731 (1996). [CrossRef] [PubMed]

4

4. T. N. Kim, K. Campbell, A. Groisman, D. Kleinfeld, and C. B. Schaffer, “Femtosecond laser-drilled capillary integrated into a microfluidic device,” Appl. Phys. Lett. 86, 201106 (2005). [CrossRef]

]. When femtosecond laser pulses are tightly focused within a transparent bulk material, nonlinear absorption can be induced in the focal volume and lead to highly localized energy deposition resulting a range of possible changes in material properties. This highly localized modification gives femtosecond laser micromachining a unique 3D microfabrication capability, and has been used to create volume optical storage [5

5. E. N. Glezer, M. Milosavljevic, L. Huang, R. J. Finlay, T. H. Her, J. P. Callan, and E. Mazur, “Threedimensional optical storage inside transparent materials,” Opt. Lett. 21, 2023–2025 (1996). [CrossRef] [PubMed]

, 6

6. B. H. Cumpston, S. P. Ananthavel, S. Barlow, D. L. Dyer, J. E. Ehrlich, L. L. Erskine, A. A. Heikal, S. M. Kuebler, I. Y. S. Lee, D. McCord-Maughon, J. Q. Qin, H. Rockel, M. Rumi, X. L. Wu, S. R. Marder, and J. W. Perry, “Two-photon polymerization initiators for three-dimensional optical data storage and microfabrication,” Nature 398, 51–54 (1999). [CrossRef]

], gratings [7

7. J. H. Si, J. R. Qiu, J. F. Zhai, Y. Q. Shen, and K. Hirao, “Photoinduced permanent gratings inside bulk azodye-doped polymers by the coherent field of a femtosecond laser,” Appl. Phys. Lett. 80, 359–361 (2002). [CrossRef]

, 8

8. L. Ding, R. Blackwell, J. F. Künzler, and W. H. Knox, “Large refractive index change in silicone-based and non-silicone-based hydrogel polymers induced by femtosecond laser micro-machining,” Opt. Express 14, 11901–11909 (2006), http://www.opticsinfobase.org/abstract.cfm?URI=oe-14-24-11901. [CrossRef] [PubMed]

], waveguides [1

1. K. M. Davis, K. Miura, N. Sugimoto, and K. Hirao, “Writing waveguides in glass with a femtosecond laser,” Opt. Lett. 21, 1729–1731 (1996). [CrossRef] [PubMed]

, 9

9. A. Zoubir, C. Lopez, M. Richardson, and K. Richardson, “Femtosecond laser fabrication of tubular waveguides in poly(methyl methacrylate),” Opt. Lett. 29, 1840–1842 (2004). [CrossRef] [PubMed]

12

12. L. Ding, R. I. Blackwell, J. F. Kunzler, and W. H. Knox, “Femtosecond laser micromachining of waveguides in silicone-based hydrogel polymers,” Appl. Opt. 47, 3100–3108 (2008). [CrossRef] [PubMed]

], photonic bandgap structures [13

13. M. Straub and M. Gu, “Near-infrared photonic crystals with higher-order bandgaps generated by twophoton photopolymerization,” Opt. Lett. 27, 1824–1826 (2002). [CrossRef]

17

17. W. Haske, V. W. Chen, J. M. Hales, W. T. Dong, S. Barlow, S. R. Marder, and J. W. Perry, “65 nm feature sizes using visible wavelength 3-D multiphoton lithography,” Opt. Express 15, 3426–3436 (2007), http://www.opticsexpress.org/abstract.cfm?URI=OPEX-15-6-3426. [CrossRef] [PubMed]

] and microfluidic devices [4

4. T. N. Kim, K. Campbell, A. Groisman, D. Kleinfeld, and C. B. Schaffer, “Femtosecond laser-drilled capillary integrated into a microfluidic device,” Appl. Phys. Lett. 86, 201106 (2005). [CrossRef]

, 18

18. D. Day and M. Gu, “Microchannel fabrication in PMMA based on localized heating by nanojoule high repetition rate femtosecond pulses,” Opt. Express 13, 5939–5946 (2005), http://www.opticsexpress.org/abstract.cfm?URI=OPEX-13-16-5939. [CrossRef] [PubMed]

].

Recently, this technology has been employed to fabricate photonic structures in various polymer materials. Many different mechanisms can be induced by femtosecond laser micromachining in polymer materials. For various photoresists or polymer resins, two-photon polymerization is the major mechanism that is induced by femtosecond laser micromachining [6

6. B. H. Cumpston, S. P. Ananthavel, S. Barlow, D. L. Dyer, J. E. Ehrlich, L. L. Erskine, A. A. Heikal, S. M. Kuebler, I. Y. S. Lee, D. McCord-Maughon, J. Q. Qin, H. Rockel, M. Rumi, X. L. Wu, S. R. Marder, and J. W. Perry, “Two-photon polymerization initiators for three-dimensional optical data storage and microfabrication,” Nature 398, 51–54 (1999). [CrossRef]

, 13

13. M. Straub and M. Gu, “Near-infrared photonic crystals with higher-order bandgaps generated by twophoton photopolymerization,” Opt. Lett. 27, 1824–1826 (2002). [CrossRef]

, 15

15. P. Yao, G. J. Schneider, D. W. Prather, E. D. Wetzel, and D. J. O’Brien, “Fabrication of three-dimensional photonic crystals with multilayer photolithography,” Opt. Express 13, 2370–2376 (2005), http://www.opticsexpress.org/abstract.cfm?URI=OPEX-13-7-2370. [CrossRef] [PubMed]

17

17. W. Haske, V. W. Chen, J. M. Hales, W. T. Dong, S. Barlow, S. R. Marder, and J. W. Perry, “65 nm feature sizes using visible wavelength 3-D multiphoton lithography,” Opt. Express 15, 3426–3436 (2007), http://www.opticsexpress.org/abstract.cfm?URI=OPEX-15-6-3426. [CrossRef] [PubMed]

, 19

19. J. Serbin, A. Egbert, A. Ostendorf, B. N. Chichkov, R. Houbertz, G. Domann, J. Schulz, C. Cronauer, L. Frohlich, and M. Popall, “Femtosecond laser-induced two-photon polymerization of inorganic-organic hybrid materials for applications in photonics,” Opt. Lett. 28, 301–303 (2003). [CrossRef] [PubMed]

]. Monomers within these materials with lower degree of polymerization can be highly polymerized through this mechanism and thereby form polymer structures. Post-exposure treatments such as thermal bake are usually needed to realize full polymerization. Recent research has shown that photoinitiators or chromophores with large two-photon absorption (TPA) cross-sections can help to enhance polymerization rates during the femtosecond micromachining process [6

6. B. H. Cumpston, S. P. Ananthavel, S. Barlow, D. L. Dyer, J. E. Ehrlich, L. L. Erskine, A. A. Heikal, S. M. Kuebler, I. Y. S. Lee, D. McCord-Maughon, J. Q. Qin, H. Rockel, M. Rumi, X. L. Wu, S. R. Marder, and J. W. Perry, “Two-photon polymerization initiators for three-dimensional optical data storage and microfabrication,” Nature 398, 51–54 (1999). [CrossRef]

, 17

17. W. Haske, V. W. Chen, J. M. Hales, W. T. Dong, S. Barlow, S. R. Marder, and J. W. Perry, “65 nm feature sizes using visible wavelength 3-D multiphoton lithography,” Opt. Express 15, 3426–3436 (2007), http://www.opticsexpress.org/abstract.cfm?URI=OPEX-15-6-3426. [CrossRef] [PubMed]

]. Femtosecond lasers are also employed to micromachine polymer materials that are fully polymerized such as poly(methylmethacrylate) (PMMA) and polystyrene (PS) [7

7. J. H. Si, J. R. Qiu, J. F. Zhai, Y. Q. Shen, and K. Hirao, “Photoinduced permanent gratings inside bulk azodye-doped polymers by the coherent field of a femtosecond laser,” Appl. Phys. Lett. 80, 359–361 (2002). [CrossRef]

, 9

9. A. Zoubir, C. Lopez, M. Richardson, and K. Richardson, “Femtosecond laser fabrication of tubular waveguides in poly(methyl methacrylate),” Opt. Lett. 29, 1840–1842 (2004). [CrossRef] [PubMed]

11

11. C. R. Mendonca, L. R. Cerami, T. Shih, R. W. Tilghman, T. Baldacchini, and E. Mazur, “Femtosecond laser waveguide micromachining of PMMA films with azoaromatic chromophores,” Opt. Express 16, 200–206 (2008), http://www.opticsinfobase.org/abstract.cfm?URI=oe-16-1-200. [CrossRef] [PubMed]

, 20

20. S. Katayama, M. Horiike, K. Hirao, and N. Tsutsumi, “Structures induced by irradiation of femto-second laser pulse in polymeric materials,” J. Polym. Sci. Polym. Phys. 40, 537–544 (2002). [CrossRef]

23

23. X. P. Li, J. W. M. Chon, S. H. Wu, R. A. Evans, and M. Gu, “Rewritable polarization-encoded multilayer data storage in 2,5-dimethyl-4-(p-nitrophenylazo)anisole doped polymer,” Opt. Lett. 32, 277–279 (2007). [CrossRef] [PubMed]

]. Femtosecond laser-induced photochemical modifications such as polymer backbone cleavage and chain unzipping cause the refractive index (RI) changes in pure PMMA [24]. Recently, PMMA doped with various dyes has also been studied for structural modifications and device fabrication with RI changes ranging from 10-4 to 10-3 through femtosecond laser micromachining [7

7. J. H. Si, J. R. Qiu, J. F. Zhai, Y. Q. Shen, and K. Hirao, “Photoinduced permanent gratings inside bulk azodye-doped polymers by the coherent field of a femtosecond laser,” Appl. Phys. Lett. 80, 359–361 (2002). [CrossRef]

, 11

11. C. R. Mendonca, L. R. Cerami, T. Shih, R. W. Tilghman, T. Baldacchini, and E. Mazur, “Femtosecond laser waveguide micromachining of PMMA films with azoaromatic chromophores,” Opt. Express 16, 200–206 (2008), http://www.opticsinfobase.org/abstract.cfm?URI=oe-16-1-200. [CrossRef] [PubMed]

, 21

21. S. Katayama, M. Horiike, K. Hirao, and N. Tsutsumi, “Structure induced by irradiation of femtosecond laser pulse in dyed polymeric materials,” J. Polym. Sci. Polym. Phys. 40, 2800–2806 (2002). [CrossRef]

, 25

25. Y. P. Meshalkin, V. A. Svetlichnyi, A. V. Reznichenko, A. Y. Myachin, S. S. Bakhareva, S. M. Dolotov, T. N. Kopylova, and E. P. Ponomarenko, “Two-photon excitation of dyes in a polymer matrix by femtosecond pulses from a Ti:sapphire laser,” Quantum Electron. 33, 803–806 (2003). [CrossRef]

].

Fig. 1. Molecular structures of major compositions within the hydrogel polymers

2. Experimental Setup

Two typical kinds of ophthalmologic hydrogel polymers were studied in our experiments. Hydroxyethyl methacrylate (HEMA)-based hydrogel polymers are the second of five generations of ophthalmologic hydrogel materials [26

26. C. C. S. Karlgard, D. K. Sarkar, L. W. Jones, C. Moresoli, and K. T. Leung, “Drying methods for XPS analysis of PureVision, Focus® Night&Day and conventional hydrogel contact lens,” Appl. Surf. Sci. 230, 106–114 (2004). [CrossRef]

]. Although they were invented in 1960s, they are still widely used to make contact lenses. We studied HEMA-based hydrogel polymers with a trade name Akreos® (Bausch and Lomb) which has about 80% by weight HEMA. The water concentration of Akreos® is about 29% by weight. The others are Silicone-based hydrogel polymers, which represent the fifth and the most recent generation of ophthalmologic hydrogel materials [26

26. C. C. S. Karlgard, D. K. Sarkar, L. W. Jones, C. Moresoli, and K. T. Leung, “Drying methods for XPS analysis of PureVision, Focus® Night&Day and conventional hydrogel contact lens,” Appl. Surf. Sci. 230, 106–114 (2004). [CrossRef]

]. They have significantly improved oxygen permeability and are used to make ophthalmologic devices for long-term use with the trade name PureVision (Balafilcon A) from Bausch & Lomb. They contain tris(trimethylsiloxy)silyl propylvinyl carbamate (TPVC), N-vinyl pyrrolidone (NVP) and other silicone components. The water concentration of PureVision (Balafilcon A) is about 36% by weight. Figure 1 shows the molecular structures of these major compositions within these hydrogel polymers. During the sample doping process, Fluorescein or Coumarin 1 dye was first dissolved in an ethanol-water mixture and then solution-doped into the hydrogel polymer samples. The doping concentrations of Fluorescein and Coumarin 1 are prepared to be 0.17% and 16% respectively, which we experimentally determined gave roughly equal enhancements in writing speed. It has been reported that diluted Fluorescein and Coumarin solutions with 100µM concentration have 33–36 GM TPA cross section at 800 nm excitation wavelength, where GM (Goeppert - Meyer) is the TPA cross section unit equal to 10-50 cm4 s photon-1 mol-1 [27

27. C. Xu and W. W. Webb, “Measurement of two-photon excitation cross sections of molecular fluorophores with data from 690 to 1050 nm,” J. Opt. Soc. Am. B 13, 481–491 (1996). [CrossRef]

, 28

28. N. S. Makarov, M. Drobizhev, and A. Rebane, “Two-photon absorption standards in the 550–1600 nm excitation wavelength range,” Opt. Express 16, 4029–4047 (2008). [CrossRef] [PubMed]

]. Figure 2 shows the molecular structures of these two dyes.

Fig. 2. Molecular structures of Fluorescein and Coumarin 1

We micromachined the samples using 27-fs, 800-nm laser pulses operating at a 93 MHz repetition rate from a Kerr-lens mode-locked Ti:Sapphire femtosecond laser oscillator (K-M Labs). The focusing objective was a 60X 0.70NA Olympus LUCPlanFLN long-working-distance microscope objective which could be adjusted to create a nearly diffraction-limited laser spot at the focal point. In the experiments, the average laser power at the focal point was set as 120 mW, corresponding to pulse energies of 1.3 nJ. One pair of SF10 prisms in a double-pass configuration was used in the optical path to pre-compensate dispersion and form nearly transform-limited pulses at the focus. The hydrogel samples were mounted on a 3D scanning platform formed by three Newport VP-25XA linear servo stages [8

8. L. Ding, R. Blackwell, J. F. Künzler, and W. H. Knox, “Large refractive index change in silicone-based and non-silicone-based hydrogel polymers induced by femtosecond laser micro-machining,” Opt. Express 14, 11901–11909 (2006), http://www.opticsinfobase.org/abstract.cfm?URI=oe-14-24-11901. [CrossRef] [PubMed]

]. Different scanning speeds ranging from 0.4 µm/s to 1mm/s with respect to the laser beam were tested. After the micromachining process, RI changes within the laser machined region were measured by differential interference contrast (DIC) microscopy that we calibrated by writing diffraction gratings and measuring diffraction efficiency [8

8. L. Ding, R. Blackwell, J. F. Künzler, and W. H. Knox, “Large refractive index change in silicone-based and non-silicone-based hydrogel polymers induced by femtosecond laser micro-machining,” Opt. Express 14, 11901–11909 (2006), http://www.opticsinfobase.org/abstract.cfm?URI=oe-14-24-11901. [CrossRef] [PubMed]

].

Fig. 3. Transmission spectra of pure and doped (a) Akreos and (b) Balafilcon A. After doping with Fluorescein and Coumarin 1, the cutoff wavelengths of the hydrogel polymers shifted to above 400 nm. The laser operates at 800 nm wavelength.

3. Experiment results and discussion

The transmission spectra of 700µm-thick pure and doped hydrogel polymer samples were measured with an Ocean Optics HR4000 spectrometer (Fig. 3). Strong absorption around 400 nm is observed when pure hydrogel polymers are doped with these two dyes. All the samples are substantially transparent near 800 nm before and after doping.

Fig. 4. Refractive index change induced by femtosecond laser micromachining as a function of the scanning speed within (a) pure and doped Akreos, and (b) pure and doped Balafilcon A.

Table 1. Refractive index change as a function of the laser scanning speed

table-icon
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Akreos samples doped with Fluorescein dye ranging from 0.0625% to 0.5% were also investigated. Figure 5 shows the measured RI changes induced by 120 mW average power femtosecond laser pulses with 1mm/s scanning speed. Four Fluorescein dye concentrations of 0.0625%, 0.125%, 0.25% and 0.5% were used. As large RI change of 0.065±0.005 could be induced in the Akreos hydrogel samples doped with 0.5% Fluorescein, RI change decreased rapidly when the dye concentration dropped. For Akreos sample doped with 0.0625% Fluorescein dye, RI change was barely detected. These results were consistent with the curve shown in Fig. 4(a) that no RI change was induced in pure Akreos when the scanning speed was higher than 100µm/s, indicating the important role that the dye plays in the hydrogel polymers in determining the femtosecond laser micromachining writing speed. For undoped hydrogels, the nonlinear absorption is due to either a weak two-photon absorption, or more generally a weak higher order multi-photon absorption process, and hence we obtain the slow micromachining speeds. For dye-doped hydrogels such as those employed here, however, two-photon absorption would be the dominant nonlinear absorption process under the 800 nm excitation conditions. We have carried out preliminary experiments to measure the nonlinear absorption. We measured the transmitted light ratio with the hydrogel sample located exactly in focus and out of focus. For undoped hydrogels, we observed nonlinear absorption in the range of a few percent, however for doped hydrogels, we observed nonlinear absorptions as high as 15%, indicating significant enhancement of the nonlinear absorption. The detailed intensity dependence of refractive index changes has been studied for glasses [30

30. D. N. Nikogosyan, “Multi-photon high-excitation-energy approach to fibre grating inscription,” Meas. Sci. Technol. 18, R1–R29(2007). [CrossRef]

], and we are studying the full intensity dependence of our nonlinear absorption and index changes in order to elucidate the exact multiphoton contributions to the machining process, the results of which will be reported elsewhere. Figure 5 shows that for high scanning speeds, higher dye concentrations produce larger RI changes in the hydrogel. If the concentration is too high, (for instance, >2% Fluorescein-doping) the dye creates aggregates in the hydrogel polymers, changing the polymer’s properties and inducing enhanced irregular optical damage in the micromachining process.

Fig. 5. Refractive index (RI) changes as a function of Fluorescein doping concentration in Akreos hydrogel when 1mm/s scanning speed and 120mW laser average power is employed.
Fig. 6. Refractive index (RI) changes as a function of water concentration in Akreos hydrogel doped with 0.5% Fluorescein with 1mm/s scanning speed.

We then studied the effect of water concentration. In our experiments, 0.5% Fluorescein doped Akreos samples with three different water concentrations were also prepared and tested, and the micromachining results were compared (Fig. 6). As we described above, for the normal Akreos samples with 29% of water concentration, RI changes as large as 0.065±0.005 were observed when the Fluorescein doping concentration was 0.5% and the scanning speed was 1 mm/s. Figure 7(a) shows the phase contrast (PC) image of several micromachined grating lines inside such a normal doped Akreos sample. No optical damage was observed along these lines, and the bright field pictures were clear. When the water concentration of the doped Akreos samples was decreased to 21%, scattered optical damage spots were created along the grating lines as shown in the PC image (Fig. 7(b)). Strong plasma light emission from the focus was observed when these damage spots were being formed during the micromachining process. These damage spots could be observed under the bright field (BF) microscope as black carbonized spots, while the other RI changed parts along the grating lines could not be observed under the BF microscope. The measured RI change within these grating lines was about 0.03±0.005. Although decreasing focused laser power or increasing scanning speed to >2 mm/s prevented inducing damage, the RI change induced in these low-water-concentration Akreos samples was less than 0.005. Fluorescein doped Akreos samples with much less water concentration (12%) were further tested. Figure 7(c) shows the micromachined results in these samples while other experimental parameters were kept as the same. While much more laser-induced damage spots were induced along the grating lines, the RI changed regions became undetectable. These RI changes are <0.005 as shown in Fig. 6. These results indicate that the water content within the polymers has a great influence the femtosecond laser micromachining process. Our recent theoretical calculations show that compared with solid dry polymers, water within the hydrogel polymers has higher heat capacity and lower heat diffusivity which can prevent rapid and large temperature increase of the polymer within the laser focal volume. The laser-induced thermal accumulation can induce additional crosslinking inside the polymer structures which densifies the polymer network, resulting in large refractive index changes [29

29. L. Ding, L. G. Cancado, L. Novotny, W. H. Knox, N. Anderson, D. Jani, R. I. Blackwell, and J. F Kunzler, “Micro-Raman spectroscopy of refractive index microstructures in silicone-based hydrogel polymers created by high-repetition-rate femtosecond laser micromachining,” Submitted to J. Opt. Soc. Am. B, (2008).

]. These results are also consistent with recent report on femtosecond laser micromachining of PMMA doped azoaromatic chromophores that low laser damage threshold (Epulse<0.2nJ) and small refractive index (Δn≈1×10-4) could be observed if only solid polymer material without any water was micromachined (for instance, as in Ref [11

11. C. R. Mendonca, L. R. Cerami, T. Shih, R. W. Tilghman, T. Baldacchini, and E. Mazur, “Femtosecond laser waveguide micromachining of PMMA films with azoaromatic chromophores,” Opt. Express 16, 200–206 (2008), http://www.opticsinfobase.org/abstract.cfm?URI=oe-16-1-200. [CrossRef] [PubMed]

]).

Fig. 7. Phase contrast (PC) images of RI changed grating lines micromachined inside Akreos hydrogel polymers doped with 0.5% Fluorescein dye. 1 mm/s scanning speed was employed. Hydrogel polymer samples containing (a) 29%, (b) 21% and (c) 12% water have been tested. Scattered laser-induced damage along the grating lines is observed within the samples with lower water concentrations as shown in (b) and (c).

4. Conclusion

In conclusion, we demonstrate large enhancement of the writing speed and large RI changes during femtosecond laser micromachining in HEMA-based and silicone-based ophthalmologic hydrogel polymers doped with Fluorescein or Coumarin 1 dyes. High-repetition-rate, low-pulse-energy, 800 nm-wavelength femtosecond laser pulses from a Ti:Sapphire oscillator were employed during the experiments. The dyes that we used are known to have large two-photon absorption cross-section at near 800 nm excitation wavelength, and this provides a mechanism for increasing the nonlinear absorption in the focus region, and therefore the micromachining efficiency. By optimizing the type and the concentration of dyes, as well as the concentration of water and the laser irradiation conditions, large index changes can been obtained with rapid scanning. Our results may find applications in several fields including ophthalmology, biomedical optics, microfluidics, biosensors, or manufacturing of customized refractive or diffractive devices requiring bio-compatible polymers.

Acknowledgments

This research was supported by grants from Bausch and Lomb, Inc. and the CEIS program #0833810 at the University of Rochester.

References and links

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K. M. Davis, K. Miura, N. Sugimoto, and K. Hirao, “Writing waveguides in glass with a femtosecond laser,” Opt. Lett. 21, 1729–1731 (1996). [CrossRef] [PubMed]

2.

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5.

E. N. Glezer, M. Milosavljevic, L. Huang, R. J. Finlay, T. H. Her, J. P. Callan, and E. Mazur, “Threedimensional optical storage inside transparent materials,” Opt. Lett. 21, 2023–2025 (1996). [CrossRef] [PubMed]

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N. Tetreault, G. von Freymann, M. Deubel, M. Hermatschweiler, F. Perez-Willard, S. John, M. Wegener, and G. A. Ozin, “New route to three-dimensional photonic bandgap materials: Silicon double inversion of polymer templates,” Adv. Mater. 18, 457–460 (2006). [CrossRef]

17.

W. Haske, V. W. Chen, J. M. Hales, W. T. Dong, S. Barlow, S. R. Marder, and J. W. Perry, “65 nm feature sizes using visible wavelength 3-D multiphoton lithography,” Opt. Express 15, 3426–3436 (2007), http://www.opticsexpress.org/abstract.cfm?URI=OPEX-15-6-3426. [CrossRef] [PubMed]

18.

D. Day and M. Gu, “Microchannel fabrication in PMMA based on localized heating by nanojoule high repetition rate femtosecond pulses,” Opt. Express 13, 5939–5946 (2005), http://www.opticsexpress.org/abstract.cfm?URI=OPEX-13-16-5939. [CrossRef] [PubMed]

19.

J. Serbin, A. Egbert, A. Ostendorf, B. N. Chichkov, R. Houbertz, G. Domann, J. Schulz, C. Cronauer, L. Frohlich, and M. Popall, “Femtosecond laser-induced two-photon polymerization of inorganic-organic hybrid materials for applications in photonics,” Opt. Lett. 28, 301–303 (2003). [CrossRef] [PubMed]

20.

S. Katayama, M. Horiike, K. Hirao, and N. Tsutsumi, “Structures induced by irradiation of femto-second laser pulse in polymeric materials,” J. Polym. Sci. Polym. Phys. 40, 537–544 (2002). [CrossRef]

21.

S. Katayama, M. Horiike, K. Hirao, and N. Tsutsumi, “Structure induced by irradiation of femtosecond laser pulse in dyed polymeric materials,” J. Polym. Sci. Polym. Phys. 40, 2800–2806 (2002). [CrossRef]

22.

D. A. Higgins, T. A. Everett, A. F. Xie, S. M. Forman, and T. Ito, “High-resolution direct-write multiphoton photolithography in poly(methylmethacrylate) films,” Appl. Phys. Lett. 88, 184101 (2006). [CrossRef]

23.

X. P. Li, J. W. M. Chon, S. H. Wu, R. A. Evans, and M. Gu, “Rewritable polarization-encoded multilayer data storage in 2,5-dimethyl-4-(p-nitrophenylazo)anisole doped polymer,” Opt. Lett. 32, 277–279 (2007). [CrossRef] [PubMed]

24.

A. Baum, P. J. Scully, M. Basanta, C. L. P. Thomas, P. R. Fielden, N. J. Goddard, W. Perrie, and P. R. Chalker, “Photochemistry of refractive index structures in poly(methyl methacrylate) by femtosecond laser irradiation,” Opt. Lett. 32, 190–192 (2007). [CrossRef]

25.

Y. P. Meshalkin, V. A. Svetlichnyi, A. V. Reznichenko, A. Y. Myachin, S. S. Bakhareva, S. M. Dolotov, T. N. Kopylova, and E. P. Ponomarenko, “Two-photon excitation of dyes in a polymer matrix by femtosecond pulses from a Ti:sapphire laser,” Quantum Electron. 33, 803–806 (2003). [CrossRef]

26.

C. C. S. Karlgard, D. K. Sarkar, L. W. Jones, C. Moresoli, and K. T. Leung, “Drying methods for XPS analysis of PureVision, Focus® Night&Day and conventional hydrogel contact lens,” Appl. Surf. Sci. 230, 106–114 (2004). [CrossRef]

27.

C. Xu and W. W. Webb, “Measurement of two-photon excitation cross sections of molecular fluorophores with data from 690 to 1050 nm,” J. Opt. Soc. Am. B 13, 481–491 (1996). [CrossRef]

28.

N. S. Makarov, M. Drobizhev, and A. Rebane, “Two-photon absorption standards in the 550–1600 nm excitation wavelength range,” Opt. Express 16, 4029–4047 (2008). [CrossRef] [PubMed]

29.

L. Ding, L. G. Cancado, L. Novotny, W. H. Knox, N. Anderson, D. Jani, R. I. Blackwell, and J. F Kunzler, “Micro-Raman spectroscopy of refractive index microstructures in silicone-based hydrogel polymers created by high-repetition-rate femtosecond laser micromachining,” Submitted to J. Opt. Soc. Am. B, (2008).

30.

D. N. Nikogosyan, “Multi-photon high-excitation-energy approach to fibre grating inscription,” Meas. Sci. Technol. 18, R1–R29(2007). [CrossRef]

OCIS Codes
(140.3390) Lasers and laser optics : Laser materials processing
(160.5470) Materials : Polymers
(320.7110) Ultrafast optics : Ultrafast nonlinear optics

ToC Category:
Laser Micromachining

History
Original Manuscript: November 7, 2008
Revised Manuscript: December 14, 2008
Manuscript Accepted: December 15, 2008
Published: December 17, 2008

Virtual Issues
Vol. 4, Iss. 2 Virtual Journal for Biomedical Optics

Citation
Li Ding, Dharmendra Jani, Jeffrey Linhardt, Jay F. Künzler, Siddhesh Pawar, Glen Labenski, Thomas Smith, and Wayne H. Knox, "Large enhancement of femtosecond laser micromachining speed in dye-doped hydrogel polymers," Opt. Express 16, 21914-21921 (2008)
http://www.opticsinfobase.org/vjbo/abstract.cfm?URI=oe-16-26-21914


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References

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  17. W. Haske, V. W. Chen, J. M. Hales, W. T. Dong, S. Barlow, S. R. Marder, and J. W. Perry, "65 nm feature sizes using visible wavelength 3-D multiphoton lithography," Opt. Express 15, 3426-3436 (2007), http://www.opticsexpress.org/abstract.cfm?URI=OPEX-15-6-3426. [CrossRef] [PubMed]
  18. D. Day, and M. Gu, "Microchannel fabrication in PMMA based on localized heating by nanojoule high repetition rate femtosecond pulses," Opt. Express 13, 5939-5946 (2005), http://www.opticsexpress.org/abstract.cfm?URI=OPEX-13-16-5939. [CrossRef] [PubMed]
  19. J. Serbin, A. Egbert, A. Ostendorf, B. N. Chichkov, R. Houbertz, G. Domann, J. Schulz, C. Cronauer, L. Frohlich, and M. Popall, "Femtosecond laser-induced two-photon polymerization of inorganic-organic hybrid materials for applications in photonics," Opt. Lett. 28, 301-303 (2003). [CrossRef] [PubMed]
  20. S. Katayama, M. Horiike, K. Hirao, and N. Tsutsumi, "Structures induced by irradiation of femto-second laser pulse in polymeric materials," J. Polym. Sci. Polym. Phys. 40, 537-544 (2002). [CrossRef]
  21. S. Katayama, M. Horiike, K. Hirao, and N. Tsutsumi, "Structure induced by irradiation of femtosecond laser pulse in dyed polymeric materials," J. Polym. Sci. Polym. Phys. 40, 2800-2806 (2002). [CrossRef]
  22. D. A. Higgins, T. A. Everett, A. F. Xie, S. M. Forman, and T. Ito, "High-resolution direct-write multiphoton photolithography in poly(methylmethacrylate) films," Appl. Phys. Lett. 88, 184101 (2006). [CrossRef]
  23. X. P. Li, J. W. M. Chon, S. H. Wu, R. A. Evans, and M. Gu, "Rewritable polarization-encoded multilayer data storage in 2,5-dimethyl-4-(p-nitrophenylazo)anisole doped polymer," Opt. Lett. 32, 277-279 (2007). [CrossRef] [PubMed]
  24. A. Baum, P. J. Scully, M. Basanta, C. L. P. Thomas, P. R. Fielden, N. J. Goddard, W. Perrie, and P. R. Chalker, "Photochemistry of refractive index structures in poly(methyl methacrylate) by femtosecond laser irradiation," Opt. Lett. 32, 190-192 (2007). [CrossRef]
  25. Y. P. Meshalkin, V. A. Svetlichnyi, A. V. Reznichenko, A. Y. Myachin, S. S. Bakhareva, S. M. Dolotov, T. N. Kopylova, and E. P. Ponomarenko, "Two-photon excitation of dyes in a polymer matrix by femtosecond pulses from a Ti:sapphire laser," Quantum Electron. 33, 803-806 (2003). [CrossRef]
  26. C. C. S. Karlgard, D. K. Sarkar, L. W. Jones, C. Moresoli, and K. T. Leung, "Drying methods for XPS analysis of PureVisionTM, Focus® Night and DayTM and conventional hydrogel contact lens," Appl. Surf. Sci. 230, 106-114 (2004). [CrossRef]
  27. C. Xu and W. W. Webb, "Measurement of two-photon excitation cross sections of molecular fluorophores with data from 690 to 1050 nm," J. Opt. Soc. Am. B 13, 481-491 (1996). [CrossRef]
  28. N. S. Makarov, M. Drobizhev, and A. Rebane, "Two-photon absorption standards in the 550-1600 nm excitation wavelength range," Opt. Express 16, 4029-4047 (2008). [CrossRef] [PubMed]
  29. L. Ding, L. G. Cancado, L. Novotny, W. H. Knox, N. Anderson, D. Jani, R. I. Blackwell, and J. F. Kunzler, "Micro-Raman spectroscopy of refractive index microstructures in silicone-based hydrogel polymers created by high-repetition-rate femtosecond laser micromachining," Submitted to J. Opt. Soc. Am. B, (2008).
  30. D. N. Nikogosyan, "Multi-photon high-excitation-energy approach to fibre grating inscription," Meas. Sci. Technol. 18, R1-R29 (2007). [CrossRef]

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