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Optics Express

Optics Express

  • Editor: C. Martijn de Sterke
  • Vol. 16, Iss. 24 — Nov. 24, 2008
  • pp: 20073–20080
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Engineering stop gaps of inorganic-organic polymeric 3D woodpile photonic crystals with post-thermal treatment

Jiafang Li, Baohua Jia, and Min Gu  »View Author Affiliations


Optics Express, Vol. 16, Issue 24, pp. 20073-20080 (2008)
http://dx.doi.org/10.1364/OE.16.020073


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Abstract

A method is reported for improving the spatial resolution and engineering the stop gaps of the inorganic-organic 3D woodpile photonic crystals (PhCs). The approach is based on the two-photon polymerization (2PP) of an inorganic-organic hybrid material and a post-thermal treatment (PTT) process. The effects of PTT on polymerized 1D, 2D and 3D structures have been characterized. Ultimately, the feature size of the suspended rods has been reduced to ~33 nm and the spatial resolution of inorganic-organic 3D woodpile PhCs has been improved from ~150 nm to ~86 nm. The approach is also demonstrated as a powerful tool to engineer the stop gaps of 3D PhCs. In particular, a combination of PTT and the threshold fabrication technique leads to the stop gap of a 3D woodpile PhC that can be tuned over a large wavelength range of ~318 nm from the near-infrared to visible region.

© 2008 Optical Society of America

1. Introduction

Direct laser writing (DLW) is an effective and flexible approach to inducing two-photon polymerization (2PP) in various photoresists and has been intensively studied for the fabrication of three-dimensional (3D) arbitrary micro-structures including 3D photonic crystals (PhCs) [1

1. S. Maruo, O. Nakamura, and S. Kawata, “Three-dimensional microfabrication with two-photon-absorbed photopolymerization,” Opt. Lett. 22, 132–134 (1997). [CrossRef] [PubMed]

10

10. J. Li, B. Jia, G. Zhou, and M. Gu, “Fabrication of three-dimensional woodpile photonic crystals in a PbSe quantum dot composite material,” Opt. Express 14, 10740–10745 (2006). [CrossRef] [PubMed]

]. The use of all-organic materials such as SCR and SU-8 [1

1. S. Maruo, O. Nakamura, and S. Kawata, “Three-dimensional microfabrication with two-photon-absorbed photopolymerization,” Opt. Lett. 22, 132–134 (1997). [CrossRef] [PubMed]

,5

5. M. Deubel, G. Von Freymann, M. Wegener, S. Pereira, K. Busch, and C. M. Soukoulis, “Direct laser writing of three-dimensional photonic-crystal templates for telecommunications,” Nat. Mater. 3, 444–447 (2004). [CrossRef] [PubMed]

] can not only produce 3D PhCs with stop gaps in the near-infrared (NIR) wavelength range [4

4. M. Straub and M. Gu, “Near-infrared photonic crystals with higher-order bandgaps generated by two-photon photopolymerization,” Opt. Lett. 27, 1824–1825 (2002). [CrossRef]

7

7. L. H. Nguyen, M. Straub, and M. Gu, “Acrylate-based photopolymer for two-photon microfabrication and photonic applications,” Adv. Funct. Mater. 15, 209–216 (2005). [CrossRef]

], but also serve as templates for further preparations of “inverted” PhCs with high refractive index [11

11. N. Tetreault, G. V. 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).

,12

12. B. Jia, S. Wu, J. Li, and M. Gu, “Near-infrared high refractive-index three-dimensional inverse woodpile photonic crystals generated by a sol-gel process,” J. Appl. Phys. 102, 096102 (2007). [CrossRef]

]. Though the feature size of the two-dimensional (2D) polymerized rods can be reduced down to less than 30 nm by employing pre-treatment methods [13

13. K. Takada, H.-B. Sun, and S. Kawata, “Improved spatial resolution and surface roughness in photopolymerization-based laser nanowriting,” Appl. Phys. Lett. 86, 1 (2005). [CrossRef]

15

15. D. Tan, Y. Li, F. Qi, H. Yang, Q. Gong, X. Dong, and X. Duan, “Reduction in feature size of two-photon polymerization using SCR500,” Appl. Phys. Lett. 90, 071106 (2007). [CrossRef]

], their poor thermal and mechanical stability [13

13. K. Takada, H.-B. Sun, and S. Kawata, “Improved spatial resolution and surface roughness in photopolymerization-based laser nanowriting,” Appl. Phys. Lett. 86, 1 (2005). [CrossRef]

,16

16. S. Juodkazis, V. Mizeikis, K. K. Seet, H. Misawa, and U. G. K. Wegst, “Mechanical properties and tuning of three-dimensional polymeric photonic crystals,” Appl. Phys. Lett. 91, 241904 (2007). [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). [CrossRef] [PubMed]

] makes them less applicable for fabricating 3D PhCs and 3D templates of high quality [18

18. Y. Jun, P. Nagpal, and D. J. Norris, “Thermally stable organic-Inorganic hybrid photoresists for fabrication of photonic band gap structures with direct laser writing,” Adv. Mater. 20, 606–610 (2008). [CrossRef]

]. These problems do not exist in all-inorganic photoresists, such as chalcogenide glasses [8

8. S. Wong, M. Deubel, F. Pérez-Willard, S. John, G. A. Ozin, M. Wegener, and G. von Freymann, “Direct laser writing of three-dimensional photonic crystals with a complete photonic bandgap in chalcogenide glasses,” Adv. Mater. 18, 265–269 (2006). [CrossRef]

]. However, the feature size of the fabricated 3D PhCs is much poorer than the diffraction limit of the laser writing beam because of the high refractive index of those materials, which restricts the writing depth and increases the structure distortion due to optical aberrations [8

8. S. Wong, M. Deubel, F. Pérez-Willard, S. John, G. A. Ozin, M. Wegener, and G. von Freymann, “Direct laser writing of three-dimensional photonic crystals with a complete photonic bandgap in chalcogenide glasses,” Adv. Mater. 18, 265–269 (2006). [CrossRef]

]. The inorganic-organic hybrid materials [9

9. J. Serbin, A. Egbert, A. Ostendorf, B. N. Chichkov, R. Houbertz, G. Domann, J. Schulz, C. Cronauer, L. Fröhlich, 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]

,10

10. J. Li, B. Jia, G. Zhou, and M. Gu, “Fabrication of three-dimensional woodpile photonic crystals in a PbSe quantum dot composite material,” Opt. Express 14, 10740–10745 (2006). [CrossRef] [PubMed]

,18

18. Y. Jun, P. Nagpal, and D. J. Norris, “Thermally stable organic-Inorganic hybrid photoresists for fabrication of photonic band gap structures with direct laser writing,” Adv. Mater. 20, 606–610 (2008). [CrossRef]

] combine the advantages of both organic and inorganic materials. With the reliable thermal and mechanical stability, such hybrid materials have been successfully applied in the fabrication of functional 3D PhCs [19

19. J. Serbin and M. Gu, “Experimental evidence for superprism effects in three-dimensional polymer photonic crystals,” Adv. Mater. 18, 221–224 (2006). [CrossRef]

22

22. J. Li, B. Jia, G. Zhou, and M. Gu, “Direction-dependent spontaneous emission from near-infrared quantum dots at the angular band edges of a three-dimensional photonic crystal,” Appl. Phys. Lett. 91, 254101 (2007). [CrossRef]

]. However the incorporation of the inorganic part in the polymerized structures has limited the fabrication resolution to approximately 150 nm [20

20. J. Serbin and M. Gu, “Superprism phenomena in waveguide-coupled woodpile structures fabricated by two-photon polymerization,” Opt. Express 14, 3563–3568 (2006). [CrossRef] [PubMed]

].

Here we use a post-thermal treatment (PTT) method to improve the spatial resolution of the 3D 2PP fabrication in an inorganic-organic hybrid material. Ultimately, the feature size of the suspended rods is reduced to ~33 nm and the spatial resolution of 3D woodpile PhCs is improved to ~86 nm. Moreover, the PTT process can efficiently engineer the stop gaps of the PhCs. A combination of PTT and the threshold fabrication technique leads to the stop gap of a 3D woodpile PhC that can be tuned over a large wavelength range of 318 nm from the NIR to visible region.

2. Experimental details

Film samples for material characterizations were prepared by illuminating spin-coated photosensitive resins on cover glass with a UV lamp, followed by washing with 4-methyl-2- pentanone and rinsing with isopropanol [9

9. J. Serbin, A. Egbert, A. Ostendorf, B. N. Chichkov, R. Houbertz, G. Domann, J. Schulz, C. Cronauer, L. Fröhlich, 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]

,19

19. J. Serbin and M. Gu, “Experimental evidence for superprism effects in three-dimensional polymer photonic crystals,” Adv. Mater. 18, 221–224 (2006). [CrossRef]

]. The photosensitive resin we used is Ormocer® which is a kind of the silicate-based inorganic-organic hybrid material. The polymerized structures are stable upon heating at temperature (T) up to 270°C [23

23. R. Buestrich, F. Kahlenberg, M. Popall, P. Dannberg, R. Müller-Fiedler, and O. Rösch, “ORMOCER®s for optical interconnection technology,” J. Sol-Gel Sci. Technol. 20, 181–186 (2001). [CrossRef]

]. Before the PTT process, the polymerized films (and all the following samples fabricated by 2PP) were hard-baked at 150°C for 3 h. Then the samples were put onto a hot plate under certain temperature for the PTT process. After each heating process, the samples were naturally cooled down to room temperature for measurements. The absorption spectra of the polymerized films were characterized with a Fourier-transform IR spectrometer (FTIR, Thermo Nicolet) in conjunction with an infrared microscope (Continuum).

Fig. 1. Absorption spectra of the polymerized films upon heating at temperature 300°C for different heating time. Spectra are normalized and translated for better view. The schematic on the right side is based on the observed changes in absorbance of organic functional groups.

The choosing of temperature for PTT is critical. Here the temperature we used for PTT is 300°C, where the thermal gravimetric analysis curve of Ormocer® shows a slow weight loss of less than 1% and the overall structures are stable under heating for 10 hours (h) [24

24. R. Mohamed, N. Razali, A. A. Ehsan, and S. Shaari, “Characterisation and process optimisation of photosensitive acrylates for photonics applications,” Sci. Technol. Adv. Mater. 6, 375–382 (2005). [CrossRef]

,25

25. B. Lange, J. Wagner, and R. Zentel, “Fabrication of robust high-quality ORMOCER® inverse opals,” Macromol. Rapid Commun. 27, 1746–1751 (2006). [CrossRef]

]. In fact, our PTT experiments under 300°C showed the best performance on PhC engineering among the tests with temperatures ranging from 150°C to 450°C. The reason is that at this temperature, some organic parts of the polymerized structures starts to be decomposed slowly while the inorganic part is well preserved, behaved as backbones to support the whole structure. As shown in Fig. 1, at 300°C, C-H groups belonging to alkyl terminations of Ormocer® molecules are decomposed and Si-OH group are formed [25

25. B. Lange, J. Wagner, and R. Zentel, “Fabrication of robust high-quality ORMOCER® inverse opals,” Macromol. Rapid Commun. 27, 1746–1751 (2006). [CrossRef]

]. Meanwhile, the methacrylic phase is further polymerized as depicted by the decrease in absorbance of C=O and C=C groups. As a consequence, the structures result more condensed with improved mechanical stability. Meanwhile, the refractive index of the polymerized films, measured with Becke line method [10

10. J. Li, B. Jia, G. Zhou, and M. Gu, “Fabrication of three-dimensional woodpile photonic crystals in a PbSe quantum dot composite material,” Opt. Express 14, 10740–10745 (2006). [CrossRef] [PubMed]

], was 1.554±0.002 before PTT and increased to 1.566±0.002 at the PTT time of 3 h and then remained nearly unchanged from 3 h to 48 h.

The micron-scale samples in the article were fabricated with 2PP method, in which femtosecond pulses (~200 fs) operating at wavelength 580 nm were focused into the photosensitive resin with an oil immersion objective (Olympus, numerical aperture 1.4, 100×) [10

10. J. Li, B. Jia, G. Zhou, and M. Gu, “Fabrication of three-dimensional woodpile photonic crystals in a PbSe quantum dot composite material,” Opt. Express 14, 10740–10745 (2006). [CrossRef] [PubMed]

,21

21. J. Li, B. Jia, G. Zhou, J. Serbin, C. Bullen, and M. Gu, “Spectral redistribution in spontaneous emission from quantum-dot-infiltrated 3D woodpile photonic crystals for telecommunications,” Adv. Mater. 19, 3276–3280 (2007). [CrossRef]

]. A serial of one-dimensional (1D) and 2D structures were fabricated with variable exposure power and fabrication speed for comparison purposes. 3D woodpile PhCs of different rod spacing were fabricated with various exposure power under a constant fabrication speed of 60 µm/s [21

21. J. Li, B. Jia, G. Zhou, J. Serbin, C. Bullen, and M. Gu, “Spectral redistribution in spontaneous emission from quantum-dot-infiltrated 3D woodpile photonic crystals for telecommunications,” Adv. Mater. 19, 3276–3280 (2007). [CrossRef]

]. The transmission spectra (>900 nm) of the woodpile PhCs in the stacking direction were characterized with a pinhole-assisted FTIR [10]. The transmission spectra of PhCs which had a stop gap below wavelength 900 nm were measured with a CCD (Pixis 100, Princeton Instruments): a broadband light source (Oriel Apex QTH Source) was focused into the PhCs by an apochromatic objective and the transmitted signals were then collected by another apochromatic objective, dispersed by a spectrograph (Acton Spectropro 300i), and finally detected by the CCD. A small aperture was inserted before the back aperture of each objective to confine the divergence angle to 10o with respect to the stacking direction of the PhCs.

3. Results and discussions

3.1. PTT effects on 1D and 2D inorganic-organic structures

To study the effects of PTT on polymerized structures, firstly, we heated a laser-generated thin film for 3 h at temperature 300°C. As shown in Figs. 2(a, b), after 3-h PTT the surface roughness of the polymerized film is improved significantly by 45% from 10 to 5.5 nm, which is similar to the thermal annealing effects on other polymers [26

26. T. Kerle, Z. Lin, H. -C. Kim, and T. P. Russell, “Mobility of polymers at the air/polymer interface,” Macromol. 34, 3484–3492 (2001). [CrossRef]

]. Meanwhile, the maximum height of the features is reduced.

Fig. 2. (a, b) AFM images of the top surface of a laser-generated thin film (a) before and (b) after 3-h heating at 300°C.

The effect of PTT on the height of the polymerized structures was then tested on an array of the fabricated parallel rods with ascending heights (Fig. 3(a)). The truncated rods were heated with several steps and the sample was characterized by an atomic force microscope (AFM) after each process. As shown in Figs. 3(b–d), both the height (H) and width (W) of the rods are significantly reduced after PTT, different for rods with different initial heights (Fig. 3(d)). In particular, the amount of reduction reaches 79% for a 69.6-nm-high rod, of which the height is reduced to 14.4 nm after 36-h PTT (see another sample in the inset of Fig. 3(e)). The plots of the height ratio (H/H0), where H0 is the height of the rod before PTT, as a function of the heating time reveal that the lower the rod, the larger the reduction (see Fig. 3(e)). However, the exponential decay behavior of the plots shows that the lower rod has a decay speed slower than that of the higher one after 3 h. This is because the lower rods have larger surface-to-volume ratios, which leads to faster heat dissipation and slower PTT effects in the case of thermal conduction.

We further studied the effect of PTT on the suspended rods fabricated between two solid supporters. Figures 4(a–b) show the SEM images of the rods with a length of ~1.5 µm before and after 3-h PTT, respectively. One can see that the width of the rods is significantly reduced without cracks (the nonuniform sizes of the rods were induced by the stretches from the solid supporters [27

27. Y. Li, F. Qi, H. Yang, Q. Gong, X. Dong, and X. Duan, “Nonuniform shrinkage and stretching of polymerized nanostructures fabricated by two-photon photopolymerization,” Nanotechnology 19, 055303 (2008). [CrossRef] [PubMed]

]). For comparison, we plot the rod width before and after 3-h PTT as a function of the fabrication speed and power in Figs. 4(c–d), respectively. It can be seen that the rod width is monotonically reduced but thicker rods are reduced by a larger percentage than the thinner ones. This is because the thicker rods have a smaller surface-to-volume ratio that results in slow heat dissipation, which makes the PTT effect more efficient. One important feature of the rods after 3-h PTT is that the suspended thin rods can preserve a good mechanical property such as rods with a long length of ~5.5 µm shown in Fig. 4(e), while the reported all-organic polymer structures are less robust under such high temperature (300°C). Furthermore, it is found that the minimum rod width of ~50 nm with 2PP by direct laser writing can be efficiently reduced to ~33 nm with PTT for only 3 h, as shown in Figs. 4(f–g).

Fig. 3. (a) Schematic of truncated rods on cover glass (side view). (b) and (c) AFM images of the rods before and after 18-h PTT. (d) Corresponding cross-sections of the rods taken from (b) and (c). (e) Height ratio H/H0 as a function of the PTT time for rods with different H0. The data beyond 3 h are fitted with the exponential decay curve. The fitted decay speeds are 0.162, 0.199 and 0.223 h-1 for rods with H0 of 193, 287 and 361 nm. Inset: Cross-sections of rods before and after 36-h PTT.
Fig. 4. (a) and (b) SEM images of rods suspended between two supporters before and after 3-h PTT. (c) and (d) Rod width as a function of the fabrication speed (V) and power (P) before and after 3-h PTT. (e) SEM image of suspended rods with a length of ~5.5 µm after 3-h PTT. (f) and (g) SEM images of suspended rods with the minimum feature size survived before and after 3-h PTT.

3.2. PTT effects on inorganic-organic 3D woodpile PhCs

The reliable mechanical properties of the structures after PTT lead to a new way to engineer 3D inorganic-organic PhCs. As the images shown in Figs. 5(a–b), the periodical structures of the PhCs are well preserved after heating at 300°C for 3 and 20 h, respectively, showing a good mechanical strength under PTT. The rod spacing of the woodpile, initially designed and fabricated at 1.1 µm, was reduced to 1.0 µm after the PTT (Fig. 5(b)). Meanwhile, the measured transmission spectra of a woodpile PhC, as shown in Fig. 5(c), reveal that the center of the stop gap is shifted from 1621 to 1458 nm after 3-h PTT, indicating that the periodicity in the stacking direction is significantly reduced. Moreover, one can notice that the transmission at shorter wavelengths increases, which means less scattering losses of the heated structures due to the improved surface roughness. Another improvement is that unwanted “defects” within the stop gap, induced by the residual stresses inherent in the fabrication process, can be cured by the PTT process that release these residual stresses, as noted in Fig. 5(c).

Fig. 5. (a) and (b) SEM images of 3D woodpile PhCs after PTT for 3 and 20 h, respectively. (c) Measured transmission spectra of a 32-layer woodpile PhC in the stacking direction before and after 3-h PTT. The four areas noted by dashed circles indicate the increased transmission at shorter wavelengths. The two vertical arrows point out the “defect” within the stop gap, which disappears after PTT. (d) Baseline corrected transmission spectra of a 32-layer woodpile PhC at different heating time (from right to left): 0, 3, 6, 9, 15, 38 h. (e) Relationship between Δλcc0 and the heating time. Experimental data beyond 3 h are fitted well with the exponential decay model with a decay speed of 0.117 h-1. Inset: Microscope image of the PhC after PTT. The outer dashed square and the inner solid square mark the woodpile before and after heating for 38 h, respectively.

It should be emphasized that the measured transmission spectra of the PhCs were very sensitive to the structure geometry. Any effect of PTT, including the influence of the substrate, can be reflected in the changes of stop gaps of PhCs. Deviation of PTT temperature from 300°C would result in no engineering effects (T<300°C) or distortions of the stop gaps (T>300°C). That is why it is very important to perform the PTT process at 300°C to realize symmetric engineering of PhCs.

3.3. Improving the spatial resolution of inorganic-organic 3D woodpile PhCs

Fig. 6. (a) Measured transmission spectra of a 20-layer woodpile PhC with a rod spacing of 700 nm. The centers of the stop gaps before and after 21-h heating are located at wavelengths 1007 and 746 nm, respectively. (b) and (c) Measured transmission spectra of 20-layer PhCs with rod spacings of 800 and 700 nm after PTT for 21 and 6 h, respectively. The centers of the stop gaps are located at wavelengths 831 and 723 nm, respectively. Inset of (c): SEM image of the PhC in (c). The width of the rod is reduced to ~86 nm.

The combination of PTT and the threshold laser writing method [2

2. S. Kawata, H. B. Sun, T. Tanaka, and K. Takada, “Finer features for functional microdevices,” Nature 412, 697–698 (2001). [CrossRef] [PubMed]

,3

3. S. Wu, J. Serbin, and M. Gu, “Two-photon polymerisation for three-dimensional micro-fabrication,” J. Photochem. Photobiol., A 181, 1–11 (2006). [CrossRef]

,19

19. J. Serbin and M. Gu, “Experimental evidence for superprism effects in three-dimensional polymer photonic crystals,” Adv. Mater. 18, 221–224 (2006). [CrossRef]

] can improve the resolution in fabricating inorganic-organic 3D PhCs and thus realize the operation in the visible wavelength range. As shown in Fig. 6(a), the stop gap of a 700-nm-lattice woodpile PhC, fabricated by the threshold method at a power of 1.3 mW, can be tuned from 1007 to 746 nm after 21-h PTT. For comparison, a PhC with a rod spacing of 800 nm was fabricated along with the 700-nm PhC and experienced the same process. As shown in Fig. 6(b), its stop gap was finally tuned to 831 nm but shows a smoother and deeper gap than that in Fig. 6(a), which reveals that the PhC with a larger lattice constant can maintain better performance for long-time PTT. Moreover, the appearance of a higher order gap [4

4. M. Straub and M. Gu, “Near-infrared photonic crystals with higher-order bandgaps generated by two-photon photopolymerization,” Opt. Lett. 27, 1824–1825 (2002). [CrossRef]

] at wavelength 531 nm (in Fig. 6(b)) indicates that the symmetry of the woodpile is well preserved. The SEM image depicted in the inset of Fig. 6(c) shows that the width of the rods of the 3D PhC can be reduced to ~86 nm, which is reduced by a factor of two compared with the previously reported value of ~150 nm in the inorganic-organic hybrid polymer [20

20. J. Serbin and M. Gu, “Superprism phenomena in waveguide-coupled woodpile structures fabricated by two-photon polymerization,” Opt. Express 14, 3563–3568 (2006). [CrossRef] [PubMed]

].

4. Conclusions

In conclusion, we have proposed and demonstrated a PTT method to improve the fabrication resolution of the structures fabricated with 2PP in inorganic-organic hybrid materials. In the cases of the 2D truncated rods on cover glass, the 2D suspended rods and the 3D woodpile PhCs, the limits of the feature size reach ~14.4, ~33 and ~86 nm, respectively. This PTT method results structures with high mechanical stability and has been successfully applied to substantially tune the stop gaps of the woodpile PhCs. In particular, a continuous 251-nm-tuning range of the stop gap of a 3D PhC has been achieved. The integration of this PTT method with the threshold fabrication method has resulted in a 3D woodpile PhC operating at visible wavelengths. This work provides a useful option for producing smaller templates for the fabrication of NIR or visible high refractive-index inverse woodpile PhCs [11

11. N. Tetreault, G. V. 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).

,12

12. B. Jia, S. Wu, J. Li, and M. Gu, “Near-infrared high refractive-index three-dimensional inverse woodpile photonic crystals generated by a sol-gel process,” J. Appl. Phys. 102, 096102 (2007). [CrossRef]

] as well as a constructive platform for promising applications of 3D visible woodpile PhCs. Varying the ratio between organic and inorganic parts in the hybrid polymers provides another dimension to engineer the structures to meet different demands through a temperature-dependent PTT process.

Acknowledgment

The authors thank Dr. Dario Buso for useful discussions in FTIR spectrum analysis. This work was produced with the assistance of the Australian Research Council under the ARC Centres of Excellence program. CUDOS (the Centre for Ultrahigh-bandwidth Devices for Optical Systems) is an ARC Centre of Excellence.

References and links

1.

S. Maruo, O. Nakamura, and S. Kawata, “Three-dimensional microfabrication with two-photon-absorbed photopolymerization,” Opt. Lett. 22, 132–134 (1997). [CrossRef] [PubMed]

2.

S. Kawata, H. B. Sun, T. Tanaka, and K. Takada, “Finer features for functional microdevices,” Nature 412, 697–698 (2001). [CrossRef] [PubMed]

3.

S. Wu, J. Serbin, and M. Gu, “Two-photon polymerisation for three-dimensional micro-fabrication,” J. Photochem. Photobiol., A 181, 1–11 (2006). [CrossRef]

4.

M. Straub and M. Gu, “Near-infrared photonic crystals with higher-order bandgaps generated by two-photon photopolymerization,” Opt. Lett. 27, 1824–1825 (2002). [CrossRef]

5.

M. Deubel, G. Von Freymann, M. Wegener, S. Pereira, K. Busch, and C. M. Soukoulis, “Direct laser writing of three-dimensional photonic-crystal templates for telecommunications,” Nat. Mater. 3, 444–447 (2004). [CrossRef] [PubMed]

6.

K. K. Seet, V. Mizeikis, S. Matsuo, S. Juodkazis, and H. Misawa, “Three-dimensional spiral-architecture photonic crystals obtained by direct laser writing,” Adv. Mater. 17, 541–545 (2005). [CrossRef]

7.

L. H. Nguyen, M. Straub, and M. Gu, “Acrylate-based photopolymer for two-photon microfabrication and photonic applications,” Adv. Funct. Mater. 15, 209–216 (2005). [CrossRef]

8.

S. Wong, M. Deubel, F. Pérez-Willard, S. John, G. A. Ozin, M. Wegener, and G. von Freymann, “Direct laser writing of three-dimensional photonic crystals with a complete photonic bandgap in chalcogenide glasses,” Adv. Mater. 18, 265–269 (2006). [CrossRef]

9.

J. Serbin, A. Egbert, A. Ostendorf, B. N. Chichkov, R. Houbertz, G. Domann, J. Schulz, C. Cronauer, L. Fröhlich, 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]

10.

J. Li, B. Jia, G. Zhou, and M. Gu, “Fabrication of three-dimensional woodpile photonic crystals in a PbSe quantum dot composite material,” Opt. Express 14, 10740–10745 (2006). [CrossRef] [PubMed]

11.

N. Tetreault, G. V. 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).

12.

B. Jia, S. Wu, J. Li, and M. Gu, “Near-infrared high refractive-index three-dimensional inverse woodpile photonic crystals generated by a sol-gel process,” J. Appl. Phys. 102, 096102 (2007). [CrossRef]

13.

K. Takada, H.-B. Sun, and S. Kawata, “Improved spatial resolution and surface roughness in photopolymerization-based laser nanowriting,” Appl. Phys. Lett. 86, 1 (2005). [CrossRef]

14.

S. Juodkazis, V. Mizeikis, K. K. Seet, M. Miwa, and H. Misawa, “Two-photon lithography of nanorods in SU-8 photoresist,” Nanotechnology 16, 846–849 (2005). [CrossRef]

15.

D. Tan, Y. Li, F. Qi, H. Yang, Q. Gong, X. Dong, and X. Duan, “Reduction in feature size of two-photon polymerization using SCR500,” Appl. Phys. Lett. 90, 071106 (2007). [CrossRef]

16.

S. Juodkazis, V. Mizeikis, K. K. Seet, H. Misawa, and U. G. K. Wegst, “Mechanical properties and tuning of three-dimensional polymeric photonic crystals,” Appl. Phys. Lett. 91, 241904 (2007). [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). [CrossRef] [PubMed]

18.

Y. Jun, P. Nagpal, and D. J. Norris, “Thermally stable organic-Inorganic hybrid photoresists for fabrication of photonic band gap structures with direct laser writing,” Adv. Mater. 20, 606–610 (2008). [CrossRef]

19.

J. Serbin and M. Gu, “Experimental evidence for superprism effects in three-dimensional polymer photonic crystals,” Adv. Mater. 18, 221–224 (2006). [CrossRef]

20.

J. Serbin and M. Gu, “Superprism phenomena in waveguide-coupled woodpile structures fabricated by two-photon polymerization,” Opt. Express 14, 3563–3568 (2006). [CrossRef] [PubMed]

21.

J. Li, B. Jia, G. Zhou, J. Serbin, C. Bullen, and M. Gu, “Spectral redistribution in spontaneous emission from quantum-dot-infiltrated 3D woodpile photonic crystals for telecommunications,” Adv. Mater. 19, 3276–3280 (2007). [CrossRef]

22.

J. Li, B. Jia, G. Zhou, and M. Gu, “Direction-dependent spontaneous emission from near-infrared quantum dots at the angular band edges of a three-dimensional photonic crystal,” Appl. Phys. Lett. 91, 254101 (2007). [CrossRef]

23.

R. Buestrich, F. Kahlenberg, M. Popall, P. Dannberg, R. Müller-Fiedler, and O. Rösch, “ORMOCER®s for optical interconnection technology,” J. Sol-Gel Sci. Technol. 20, 181–186 (2001). [CrossRef]

24.

R. Mohamed, N. Razali, A. A. Ehsan, and S. Shaari, “Characterisation and process optimisation of photosensitive acrylates for photonics applications,” Sci. Technol. Adv. Mater. 6, 375–382 (2005). [CrossRef]

25.

B. Lange, J. Wagner, and R. Zentel, “Fabrication of robust high-quality ORMOCER® inverse opals,” Macromol. Rapid Commun. 27, 1746–1751 (2006). [CrossRef]

26.

T. Kerle, Z. Lin, H. -C. Kim, and T. P. Russell, “Mobility of polymers at the air/polymer interface,” Macromol. 34, 3484–3492 (2001). [CrossRef]

27.

Y. Li, F. Qi, H. Yang, Q. Gong, X. Dong, and X. Duan, “Nonuniform shrinkage and stretching of polymerized nanostructures fabricated by two-photon photopolymerization,” Nanotechnology 19, 055303 (2008). [CrossRef] [PubMed]

OCIS Codes
(120.6810) Instrumentation, measurement, and metrology : Thermal effects
(160.5470) Materials : Polymers
(220.4000) Optical design and fabrication : Microstructure fabrication
(230.5298) Optical devices : Photonic crystals

ToC Category:
Photonic Crystals

History
Original Manuscript: October 27, 2008
Revised Manuscript: November 13, 2008
Manuscript Accepted: November 14, 2008
Published: November 20, 2008

Citation
Jiafang Li, Baohua Jia, and Min Gu, "Engineering stop gaps of inorganic-organic polymeric 3D woodpile photonic crystals with post-thermal treatment," Opt. Express 16, 20073-20080 (2008)
http://www.opticsinfobase.org/oe/abstract.cfm?URI=oe-16-24-20073


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References

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  18. Y. Jun, P. Nagpal, and D. J. Norris, "Thermally stable organic-Inorganic hybrid photoresists for fabrication of photonic band gap structures with direct laser writing," Adv. Mater. 20, 606-610 (2008). [CrossRef]
  19. J. Serbin and M. Gu, "Experimental evidence for superprism effects in three-dimensional polymer photonic crystals," Adv. Mater. 18, 221-224 (2006). [CrossRef]
  20. J. Serbin and M. Gu, "Superprism phenomena in waveguide-coupled woodpile structures fabricated by two-photon polymerization," Opt. Express 14, 3563-3568 (2006). [CrossRef] [PubMed]
  21. J. Li, B. Jia, G. Zhou, J. Serbin, C. Bullen, and M. Gu, "Spectral redistribution in spontaneous emission from quantum-dot-infiltrated 3D woodpile photonic crystals for telecommunications," Adv. Mater. 19, 3276-3280 (2007). [CrossRef]
  22. J. Li, B. Jia, G. Zhou, and M. Gu, "Direction-dependent spontaneous emission from near-infrared quantum dots at the angular band edges of a three-dimensional photonic crystal," Appl. Phys. Lett. 91, 254101 (2007). [CrossRef]
  23. R. Buestrich, F. Kahlenberg, M. Popall, P. Dannberg, R. Müller-Fiedler, and O. Rösch, "ORMOCER®s for optical interconnection technology," J. Sol-Gel Sci. Technol. 20, 181-186 (2001). [CrossRef]
  24. R. Mohamed, N. Razali, A. A. Ehsan, and S. Shaari, "Characterisation and process optimisation of photosensitive acrylates for photonics applications," Sci. Technol. Adv. Mater. 6, 375-382 (2005). [CrossRef]
  25. B. Lange, J. Wagner, and R. Zentel, "Fabrication of robust high-quality ORMOCER® inverse opals," Macromol. Rapid Commun. 27, 1746-1751 (2006). [CrossRef]
  26. T. Kerle, Z. Lin, H. -C. Kim, and T. P. Russell, "Mobility of polymers at the air/polymer interface," Macromol. 34, 3484-3492 (2001). [CrossRef]
  27. Y. Li, F. Qi, H. Yang, Q. Gong, X. Dong, and X. Duan, "Nonuniform shrinkage and stretching of polymerized nanostructures fabricated by two-photon photopolymerization," Nanotechnology 19, 055303 (2008). [CrossRef] [PubMed]

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