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Virtual Journal for Biomedical Optics

Virtual Journal for Biomedical Optics

| EXPLORING THE INTERFACE OF LIGHT AND BIOMEDICINE

  • Editors: Andrew Dunn and Anthony Durkin
  • Vol. 8, Iss. 8 — Sep. 4, 2013
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Three-dimensional laser micro-sculpturing of silicone: towards bio-compatible scaffolds

Sima Rekštytė, Mangirdas Malinauskas, and Saulius Juodkazis  »View Author Affiliations


Optics Express, Vol. 21, Issue 14, pp. 17028-17041 (2013)
http://dx.doi.org/10.1364/OE.21.017028


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Abstract

Possibility to form three-dimensional (3D) micro-structures in silicone elastomer (polydimethylsiloxane; PDMS) doped with different photo-initiators was systematically investigated using direct laser writing with femtosecond laser pulses at different exposure conditions. Accuracy of the 3D structuring with resolution of ∼ 5 μm and a fabrication throughput of ∼720 μm3/s, which is exceeding the previously reported values by ∼ 300×, was achieved. Practical recording velocities of ∼ 1 mm/s were used in PDMS with isopropyl-9H-thioxanthen-9-one (ISO) and thioxanthen-9-one (THIO) photo-initiators which both have absorption at around 360 nm wavelength. The 3D laser fabrication in PDMS without any photo-initiator resulting in a fully bio-compatible material has been achieved for the first time. Rates of multi-photon absorption and avalanche for the structuring of silicone are revealed: the two-photon absorption is seeding the avalanche of a radical generation for subsequent cross-linking. Direct writing enables a maskless manufacturing of molds for soft-lithography and 3D components for microfluidics as well as scaffolds for grafts in biomedical applications.

© 2013 OSA

1. Introduction

Silicone or polydimethylsiloxane (PDMS) is an attractive material in microfluidics, micromechanics and biology for its mechanical elasticity [1

1. J. Lotters, W. Olthuis, P. Veltink, and P. Bergveld, “The mechanical properties of the rubber elastic polymer polydimethylsiloxane for sensor applications,” J. Micromech. Microeng. 7, 145–147 (2006) [CrossRef] .

] and biocompatibility [2

2. J. Lee, X. Jiang, D. Ryan, and G. Whitesides, “Compatibility of mammalian cells on surfaces of poly(dimethylsiloxane),” Langmuir 20, 11684–11691 (2004) [CrossRef] [PubMed] .

]. It enables encapsulation of fluidic chips [3

3. T. Thorsen, S. Maerkl, and S. Quake, “Microfluidic large scale integration,” Science 298, 580–584 (2002) [CrossRef] [PubMed] .

] as well as viable cells [4

4. E. Leclerc, Y. Sakai, and T. Fujii, “Cell culture in 3-dimensional microfluidic structure of PDMS (polydimethylsiloxane),” Biomed. Microdev. 5, 109–114 (2003) [CrossRef] .

], production of mechanically tunable microlenses [5

5. N.-T. Nguyen, “Micro-optofluidic lenses: a review,” Biomicrofluidics 4, 031501 (2010) [CrossRef] [PubMed] .

, 6

6. A. Werber and H. Zappe, “Tunable microfluidic microlenses,” Appl. Opt. 44, 3238–3245 (2005) [CrossRef] [PubMed] .

] and flexible scaffolds [7

7. J.-H. Jang, C. Ullal, T. Gorishnyy, V. Tsukruk, and E.L. Thomas, “Mechanically tunable three-dimensional elastomeric network/air structures via interference lithography,” Nano Lett. 6, 740–743 (2006) [CrossRef] [PubMed] .

]. For a functional usage of PDMS in compact microdevices it is necessary, first, to precisely structure it, preferably in all three-dimensions. Then, a soft-lithography molding technique can be applied for a planar imprinting of various templates [8

8. B. Gates, Q. Xu, J. Love, D. Wolfe, and G. Whitesides, “Unconventional nanofabrication,” Annu. Rev. Mater. Res. 34, 339–372 (2004) [CrossRef] .

] for microfluidics and cell cultures.

It has been demonstrated that PDMS can be laser structured using a direct writing with appropriate photo-initiators [9

9. C. Coenjarts and C. Ober, “Two-photon three-dimensional microfabrication of poly(dimethylsiloxane) elastomers,” Chem. Mater. 16, 5556–5558 (2004) [CrossRef] .

, 10

10. T. Hasegawa, K. Oishi, and S. Maruo, “Three-dimensional microstructuring of PDMS by two-photon microstereolithography,” IEEE 06, 158–161 (2006).

] and thermo-initiators [11

11. H. Selvaraj, B. Tan, and K. Venkatakrishnan, “Maskless direct micro-structuring of pdms by femtosecond laser localized rapid curing,” J. Micromech. Microeng. 21, 075018 (2011) [CrossRef] .

]. However, the achieved throughput for the surface and volume structuring at ∼ 6 μm2/s and ∼ 12 μm3/s, respectively, (estimated from the reported data [9

9. C. Coenjarts and C. Ober, “Two-photon three-dimensional microfabrication of poly(dimethylsiloxane) elastomers,” Chem. Mater. 16, 5556–5558 (2004) [CrossRef] .

, 10

10. T. Hasegawa, K. Oishi, and S. Maruo, “Three-dimensional microstructuring of PDMS by two-photon microstereolithography,” IEEE 06, 158–161 (2006).

]) are still far too small to meet the requirements for practical applications, especially, for bio-scaffolds, where larger volumes of micro-porous templates are required. Much higher volume throughput ∼ 8.75 × 106μm3/s has been demonstrated in fabrication of 3D polymeric scaffolds out of Ormocore b59 [12

12. P. Danilevicius, S. Rekstyte, E. Balciunas, A. Kraniauskas, R. Jarasiene, R. Sirmenis, D. Baltriukiene, V. Bukelskiene, R. Gadonas, and M. Malinauskas, “Micro-structured polymer scaffolds fabricated by direct laser writing for tissue engineering,” J. Biomed. Optics 17, 081405 (2012) [CrossRef] .

] and micro-optical elements in SZ2080 resist [13

13. M. Malinauskas, A. Zukauskas, V. Purlys, K. Belazaras, A. Momot, D. Paipulas, R. Gadonas, A. Piskarskas, H. Gilbergs, A. Gaidukeviciute, I. Sakellari, M. Farsari, and S. Juodkazis, “Femtosecond laser polymerization of hybrid/integrated micro-optical elements and their characterization,” J. Opt. 12, 124010 (2010) [CrossRef] .

] where a high optical quality of surfaces is required and a surface-defining laser scan is complimented with a uniform post-development exposure by a UV-lamp. So far, those structuring velocities are not demonstrated in bio-compatible photo-polymers despite the technical capabilities of scanning stages and galvano-scanners [14

14. A. Ovsianikov, M. Malinauskas, S. Schlie, B. Chichkov, S. Gittard, R. Narayan, M. Löbler, K. Sternberg, K.-P. Schmitz, and A. Haverich, “Three-dimensional laser micro- and nano-structuring of acrylated poly(ethylene glycol) materials and evaluation of their cytoxicity for tissue engineering applications,” Acta Biomater. 7, 967–974 (2011) [CrossRef] .

, 15

15. S. Turunen, E. Kapyla, K. Terzaki, J. Viitanen, C. Fotakis, M. Kellomaki, and M. Farsari, “Pico- and femtosecond laser-induced crosslinking of protein microstructures: evaluation of processability and bioactivity,” Biofabrication p. 045002 (2011) [CrossRef] [PubMed] .

]. This limitation should be overcome by a precise tuning of the light-matter interaction, by implementing protocols combining the movement of stages and scanners, and design of new photo-polymers.

Recently, advances in the direct laser writing (DLW) employing ultrashort pulses (10 fs to 10 ps) is proving to be an advantageous approach for a precise high resolution fabrication of 2D and 3D structures at an increasing throughput [16

16. M. Malinauskas, G. Kiršanskė, S. Rekštytė, T. Jonavičius, E. Kaziulionytė, L. Jonušauskas, A. Žukauskas, R. Gadonas, and A. Piskarskas, “Nanophotonic lithography: A versatile tool for manufacturing functional three-dimensional micro-/nano-objects,” Lith. J. Phys. 52, 312–326 (2012) [CrossRef] .

]. By employing the interference or direct writing, features down to ∼100 nm in spatial resolution can be obtained. Thus the DLW has became an established technique for custom fabrication of structures required in photonics [17

17. G. von Freymann, A. Ledermann, M. Thiel, I. Staude, S. Essig, K. Busch, and M. Wegener, “Three-dimensional nanostructures for photonics,” Adv. Funct. Mater. 20, 1038–1052 (2010) [CrossRef] .

, 18

18. J. Trull, L. Maigyte, V. Mizeikis, M. Malinauskas, S. Juodkazis, C. Cojocaru, M. Rutkauskas, M. Peckus, V. Sirutkaitis, and K. Staliunas, “Formation of collimated beams behind the woodpile photonic crystal,” Phys. Rev. A 84, 033812 (2011) [CrossRef] .

], micro-optics [13

13. M. Malinauskas, A. Zukauskas, V. Purlys, K. Belazaras, A. Momot, D. Paipulas, R. Gadonas, A. Piskarskas, H. Gilbergs, A. Gaidukeviciute, I. Sakellari, M. Farsari, and S. Juodkazis, “Femtosecond laser polymerization of hybrid/integrated micro-optical elements and their characterization,” J. Opt. 12, 124010 (2010) [CrossRef] .

, 19

19. E. Brasselet, M. Malinauskas, A. Žukauskas, and S. Juodkazis, “Photopolymerized microscopic vortex beam generators: precise delivery of optical orbital angular momentum,” Appl. Phys. Let. 97, 211108 (2010) [CrossRef] .

], microfluidics [20

20. S. Maruo, K. Ikuta, and H. Korogi, “Force-controllable, optically driven micromachines fabricated by single-step two-photon microstereolithography,” J. Microelectromechanic. Syst. 12, 533–539 (2003) [CrossRef] .

, 21

21. C. Schizas, V. Melissinaki, A. Gaidukeviciute, C. Reinhardt, C. Ohrt, V. Dedoussis, B. Chichkov, C. Fotakis, M. Farsari, and D. Karalekas, “On the design and fabrication by two-photon polymerization of a readily assembled micro-valve,” Int. J. Adv. Manuf. Technol. 48, 435–441 (2010) [CrossRef] .

], artificial scaffolds [12

12. P. Danilevicius, S. Rekstyte, E. Balciunas, A. Kraniauskas, R. Jarasiene, R. Sirmenis, D. Baltriukiene, V. Bukelskiene, R. Gadonas, and M. Malinauskas, “Micro-structured polymer scaffolds fabricated by direct laser writing for tissue engineering,” J. Biomed. Optics 17, 081405 (2012) [CrossRef] .

, 14

14. A. Ovsianikov, M. Malinauskas, S. Schlie, B. Chichkov, S. Gittard, R. Narayan, M. Löbler, K. Sternberg, K.-P. Schmitz, and A. Haverich, “Three-dimensional laser micro- and nano-structuring of acrylated poly(ethylene glycol) materials and evaluation of their cytoxicity for tissue engineering applications,” Acta Biomater. 7, 967–974 (2011) [CrossRef] .

], and other fields [22

22. Y.-L. Zhang, Q.-D. Chen, H. Xia, and H.-B. Sun, “Designable 3D nanofabrication by femtosecond laser direct writing,” Nano Today 5, 435–448 (2010) [CrossRef] .

]. PDMS is an attractive material for a soft-lithography molding [23

23. D. Lipomi, R. Martinez, L. Cademartiri, and G. Whitesides, “Soft lithographic approaches to nanofabrication,” Polymer Sci. 7, 211–231 (2012).

], especially for 3D and large area replication [24

24. C. LaFratta, L. Li, and J. Fourkas, “Soft-lithographic replication of 3d microstructures with closed loops,” PNAS 103, 8589–8594 (2006) [CrossRef] [PubMed] .

, 25

25. P. Danilevicius, S. Rekstyte, E. Balciunas, A. Kraniauskas, R. Sirmenis, D. Baltriukiene, V. Bukelskiene, R. Gadonas, V. Sirvydis, A. Piskarskas, and M. Malinauskas, “Laser 3D micro/nanofabrication of polymers for tissue engineering applications,” Opt. Laser Technol. 45, 518–524 (2013) [CrossRef] .

].

Here, we systematically studied and optimized a PDMS doping with prospective photo-initiators for the augmented fabrication throughput in terms of area and volume per time. The fabrication throughput was calculated by the following formulas for the 2D and 3D cases, respectively: V2D = v × dx and V3D = v × dx × dz, where v is the laser scan velocity, dx is the distance between parallel scans in x- or y-direction (lateral), dz is the distance between parallel scans in z-direction (axial). The exposure parameters of a fs-laser irradiation were tested to reveal the importance of the multi-photon and avalanche ionization at the close-to-the-dielectric-breakdown conditions; the breakdown typically occurs at 7–10 TW/cm2 in crystals and glasses under tight focusing [26

26. E. Gamaly, S. Juodkazis, V. Mizeikis, H. Misawa, A. Rode, and W. Krolokowski, “Modification of refractive index by a single fs-pulse confined inside a bulk of a photo-refractive crystal,” Phys. Rev. B 81, 054113 (2010) [CrossRef] .

28

28. E. E. Gamaly, S. Juodkazis, K. Nishimura, H. Misawa, B. Luther-Davies, L. Hallo, P. Nicolai, and V. Tikhonchuk, “Laser-matter interaction in a bulk of a transparent solid: confined micro-explosion and void formation,” Phys. Rev. B 73, 214101 (2006) [CrossRef] .

]. We show that a pure PDMS without photo-initiator can be 3D structured by solely tuning the exposure conditions of laser irradiation. A fabrication resolution typical for bio-scaffolds ∼ 5 μm was used for benchmarking different photo-initiators (the quest for the highest resolution was beyond the scope of this study).

2. Experimental

2.1. Materials

A commercial elastomeric PDMS kit (Sylgard 184, Dow Corning) was used to prepare samples for the fs-laser structuring. The pre-polymer used for the laser-induced polymerization was made by a two step process: first, photo-initiator was dissolved in a tetrahydrofuran (THF), then, solution was added to the PDMS pre-polymer and left overnight on a magnetic stirrer. For the experiments with laser setup No. 1 (Sec. 2.2), three different photo-initiators were used: namely, thioxanthen-9-one (THIO), isopropyl-9H-thioxanthen-9-one (ISO) and 2-benzyl-2-(dimethylamino)-4′-morpholinobutyrophenone (IRG2). The concentration of THIO in PDMS was 0.2 wt %, ISO – 0.2, 0.5 or 1 wt % and IRG2 – 0.5 wt %. Samples for the laser structuring were prepared by drop-casting on a cover glass substrate and then heating at ≈ 100°C temperature for 30 min to evaporate the THF solvent.

For experiments with the laser setup No. 2 (Sec. 2.2) thirteen different photo-initiators were tested:
  1. 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (Irgacure 369) – IRG1 (Ciba),
  2. 4,4′-bis(diethylamino)-benzophenone – BIS1 (Sigma Aldrich),
  3. isopropyl-9H-thioxanthen-9-one – ISO (Sigma Aldrich),
  4. lucirin TPO – TPO (BASF),
  5. lucirin TPO-L – TPO-L (BASF),
  6. 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone – HYD (Sigma Aldrich),
  7. 2-benzyl-2-(dimethylamino)-4′-morpholinobutyrophenone – BEN (Sigma Aldrich),
  8. phenylbis (2,4,6-trimethylbenzoyl)-phosphine oxide – PHE (Sigma Aldrich),
  9. (1S)-(+)-camperchinon – CAM (Sigma Aldrich),
  10. 2,2-dimethoxy-2-phenylacetophenone – DIM (Sigma Aldrich),
  11. 2-benzyl-2-(dimethylamino)-4′-morpholinobutyrophenone – IRG2 (Sigma Aldrich),
  12. 4,4′bis(dimethyl-amino)-benzophenon – BIS2 (Fluka),
  13. thioxanthen-9-one – THIO (Sigma Aldrich).

Solubility of photo-initiators in the PDMS is summarized in Table 1. The photo-initiators were dissolved, at first, in THF (except the TPO-L which is liquid, and was added to PDMS directly) and only then added to PDMS. Figure 1 shows typical absorption spectra of the samples: resin sandwiched between two cover glasses with the cover glass absorption subtracted.

Table 1. PDMS structuring with different photo-initiators (PI). Exposure conditions (laser setup No. 2): objective lens 100× magnification, numerical aperture NA = 1.4, average power Pav = 53 mW (before the lens), scan velocity vs = 10 – 40 μm/s at the repetition rate fr = 75 MHz. Overall transmission coefficient through the lens to the exposure point was T = 0.235 for the 800 nm wavelength. After the laser fabrication, samples were immersed in a methyl isobutyl ketone for ≈ 30 min to rinse the unexposed resin.

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Fig. 1 Absorption spectra of PDMS samples with different photo-initiators (see, Table 1). Absorption spectra are clipped at optical density OD = 3 (Intensity/103-level). Thickness of drop cast photo-polymer was ∼1 mm.

To avoid heat modification of the samples, the mixture was left stirring overnight at the ambient conditions for the THF evaporation. Then, before the laser fabrication a heating at ≈ 90°C for 30 min was applied for the final removal of solvent. The laser structuring experiments (setup No. 2) were performed with all the mixtures even with the ones in which photo-initiator did not dissolve completely. After laser fabrication, the samples were immersed in a methyl isobutyl ketone for ≈ 30 min to rinse the unexposed resin. Samples were inspected by a scanning electron microscopy (SEM) after applying a 10 nm conductive gold layer by sputtering.

2.2. Laser setup

We used two different fs-laser fabrication systems (see, Fig. 2(a)) which allowed us to explore effects of pulse duration, thermal accumulation and wavelength. A more detailed description of the systems can be found elsewhere [29

29. M. Malinauskas, V. Purlys, M. Rutkauskas, A. Gaidukevičiutė, and R. Gadonas, “Femtosecond visible light induced two-photon photopolymerization for 3D micro/nanostructuring in photoresists and photopolymers,” Lith. J. Phys. 50, 201–208 (2010) [CrossRef] .

, 30

30. F. Claeyssens, E. A. Hasan, A. Gaidukevičiūtė, D. S. Achilleos, A. Ranella, C. Reinhardt, A. Ovsianikov, X. Shizhou, C. Fotakis, M. Vamvakaki, B. N. Chichkov, and M. Farsari, “Production of biodegradable tissue engineering scaffold materials via 2-photon polymerisation,” Langmuir 25, 3219–3223 (2009) [CrossRef] [PubMed] .

]. The results are analyzed with a focus on the fabrication throughput and influence of photo-initiator performance rather a detailed comparison of all the used fabrication conditions. Here we list the main parameters setups.

Fig. 2 (a) Fs laser fabrication setup with in situ monitoring of fabrication (setups No.1 and 2 (Sec. 2.2) differed in wavelength, pulse duration, and sample scanning). (b) Close-up view of sample: polymerization is performed starting from the substrate’s surface, when further layers are being formed as the laser beam is focussed through previously polymerized parts of the structure. (c) Multipath scanning. A – a line is formed by several parallel laser beam scans; B – the line is scanned repeatedly along the same path to strengthen the polymerized region.

The first setup No. 1 had a fs-laser Pharos (Light Conversion) laser operating at the 1030 nm fundamental wavelength. The second harmonic at 515 nm was used for fabrication with 300 fs pulses at a 200 kHz repetition rate. The polymerization trajectory was controlled by xy-galvanometric scanners (SCANLAB hurrySCAN II 10) and a sample positioning system Aerotech ALS130-100 (x and y-axis) and ALS130-50 (z-axis) linear motion stages ensuring the positioning resolution of 50 nm. 3DPoli software took control over a laser exposure automation of the sample [31

31. 3DPoli@gmail.com.

].

The second setup No. 2 had a Ti:Sapphire fs-laser operating at a 800 nm fundamental wavelength delivering 20 fs pulses at a 75 MHz repetition rate. The beam was scanned in x and y-directions by a galvano-mirror digital scanner (SCANLAB hurrySCAN II) controlled with SAMLight (SCAPS) software. A large scale lateral movement as well as the movement along z-axis was handled by step motors (PI Instruments).

In both systems fabrication was monitored in real time using a sample illumination setup consisting of a LED light and a CMOS camera. A cover glass was used as a substrate with pre-polymer pointing downwards. This allowed the use of the immersion oil objectives for laser fabrication. The peak irradiance assuming a Gaussian intensity envelope is Ip=T×2PavfrtpS while the average intensity is Iav = Ip/2. The dielectric breakdown was observed at the peak intensity Ip ≈ 1.44 TW/cm2 with setup No. 1 and Ip ≈ 5.42 TW/cm2 with setup No. 2 (for PDMS:ISO) and Ip ≈ 1.92 TW/cm2 with setup No. 1 (for PDMS:THIO) by in situ monitoring at the scanning velocities of 1 mm/s.

3. Results and discussion

The two laser setups No. 1 and 2 have different capabilities in terms of repetition rate (hence, thermal accumulation), also wavelength, and pulse duration. We benchmarked them for the fabrication throughput measure and quality of 2D and 3D structures in PDMS. The role of photo-initiator and the mechanisms of polymerization at the high irradiance were qualitatively compared. The resolution limits were not tested; we fabricated structures with resolution typical for the bio-scaffolds.

3.1. Formation of 3D structures with a 800 nm/20 fs high-repetition exposure

Table 1 summarizes the results of grid pattern fabrication in PDMS doped with different photo-initiators using λ = 800 nm and tp = 20 fs pulses at a high repetition rate (the laser setup No. 2). Very short pulses minimize thermal accumulation while the high fr = 75 MHz repetition rate allows for a thermal accumulation between subsequent pulses which depends on a scan velocity, vs. Typically at a 1.5% wt loading of photo-initiator, the resin becomes turbid and this always hampers or renders impossible the 3D structuring. Only a few initiators show promising results and 3D structures can be obtained. PDMS without photo-initiator was not polymerizable with the laser setup No. 2.

Then, we investigated if a larger amount of these photo-initiators can be dissolved in PDMS. Up to 1 % of ISO, TPO and TPO-L was dissolved without apparent change of the optical transparency. These mixtures together with those doped with THIO, IRG2 and BIS2 were then investigated using laser powers up to 90 mW (Ip ≈ 7.38 TW/cm2) for fabrication of 2D grids; we define structures being 2D if the width of the grid log/beam is comparable with its height, hence the aspect ratio far = height/width ≤ 1 and structure is 3D if far > 1. The best structuring results were obtained using ISO, although some 2D structures fabricated with THIO and IRG2 also survived the development. However, the quality of THIO and IRG2 structures as well as used velocities (40 μm/s) for their fabrication were not promising for the practical applications. Thus, the ISO doping was chosen for the further investigation.

Grids formed out of PDMS mixed with 1% wt. ISO are shown in Fig. 3. Structures were made of 6 layers staggered axially with separation Δz = 0.5 μm and hatching in lateral x- and y-directions by Δx = Δy = 0.2 μm at laser power of Pav = 64 mW (Ip ≈ 5.25 TW/cm2) and scanning velocity was vs = 150 μm/s (cumulative dose of the exposure Dac = Ep × Np ≈ 18 kJ/cm2, where number of pulses over the spot size 2w0 is Np = 2w0/(vs/fr)). This very large dose indicates that photo-polymerization is not an efficient process and this is why photo-initiation has to be used.

Fig. 3 (a,b) 2D grid fabricated in PDMS with 1% ISO. Exposure conditions: Pav = 64 mW (Ip ≈ 5.25 TW/cm2), vs = 150 μm/s (throughput of 30 μm2/s); 6 layers in z-axis dz = 0.5 μm, 0.2 μm hatching in x and y-axis. Intersections of the grid walls are taller than other areas due to double exposure dose acquired due to overlapping scanning trajectories.

Next, for fabrication of 3D structures we had to take into account that PDMS:ISO is in a liquid state, hence, polymerization has to start from the glass substrate to anchor the 3D structure (see, Fig. 2(b)). As a result, formation of the 3D pattern is carried out by focusing throughout the already polymerized regions. This introduced beam distortions and change of focusing conditions which have to be addressed. We implemented two solutions: (i) different laser power was used at a different depth and (ii) an increased exposure dose of the far-outer layers by increased number of scans (Fig. 2(c)). Results of the two strategies are shown in Fig. 4. By increasing the exposure dose of the outer (more distant axially) layers 3D structures were retrieved with structure closer to the designed pattern (see, panels (c,d)). The largest 2D and 3D throughput using the laser setup No. 2 were 30 μm2/s and 20 μm3/s, respectively.

Fig. 4 (a, b) 3D structure fabricated in PDMS:ISO 1%. Parameters used: incremental power Pav = 62 – 64 – 67 mW (Ip ≈ 5.09 – 5.25 – 5.50 TW/cm2), vs = 150 μm/s (throughput of 20 μm3/s), 30 layers in z-axis Δz = 0.5 μm, hatching laterally 0.2 μm. (c–d) 3D structure fabricated out of ISO 1%. Parameters used: Pav = 64 mW (Ip ≈ 5.25 TW/cm2) and second scanning with Pav 55 mW (Ip ≈ 4.51 TW/cm2) for the last two layers, vs = 150 μm/s (throughput of 15 μm3/s), 24 layers in z-axis Δz = 0.5 μm, hatching laterally 0.2 μm.

3.2. Formation of 3D structures with a 515 nm/300 fs sub-1 MHz repetition exposure

With the laser setup No. 1 fully 3D microstructures were fabricated out of PDMS using two different photo-initiators (THIO and ISO) using 100× magnification NA = 1.25 objective lens (transmission T = 0.14) as well as pure PDMS without photo-initiator. Experiments with different mixtures were performed by fabricating arrays of the same 3D structure changing the laser power and sample translation velocity. At first, only linear stages were used for sample translation. The distance between parallel scans in these structures in x and y-axis were 0.3 μm and the distance between layers in z-axis was 0.4 μm. The resolution of structuring achieved was ≈ 5 μm laterally and ≈ 3 μm axially. It is important to note, that higher resolution is possible to achieve but we used a typical resolution for the bio-scaffold fabrication in this study.

Fig. 5 SEM micrograph of 3D structures fabricated in PDMS. (a) THIO 0.2%. Parameters used: power Pav = 0.8 mW (Ip ≈ 1.92 TW/cm2), vs = 150 μm/s, Δz = 0.4 μm, hatching 0.3 μm. (b) ISO 0.5%. Parameters used: power Pav = 0.7 mW (Ip ≈ 1.68 TW/cm2), vs = 4 mm/s, Δz = 0.4 μm, hatching 0.3 μm. The designed models are shown in the insets.

Experiments were also performed using PDMS mixed with various quantities of ISO photo-initiator (0.2, 0.5 and 1% wt). Good quality 3D structures were made out of PDMS mixed with 0.2% and 0.5% wt ISO (Fig. 5(b)). Using 0.5% wt ISO sample translation velocity of up to 1.5 mm/s was achieved (Pav = 0.5 mW, Ip ≈ 1.20 TW/cm2, Dac ≈ 12.07 J/cm2) giving fabrication throughput of 180 μm3/s.

PDMS mixed with IRG2 was also used for laser structuring using multi-path scanning (which is proven to be the best for 3D structures as discussed above) with velocities of up to 30 μm/s and focusing with a dry 40× magnification NA = 0.65 objective lens. The acquired throughput of 2D structures was ≈ 10 μm2/s.

Pure PDMS without a photo-initiator can be 3D polymerized using translation velocity of up to 1 mm/s with Pav = 0.7 mW (Ip ≈ 1.68 TW/cm2, Dac ≈ 25.36 J/cm2) giving a fabrication throughput of 120 μm3/s as shown in Fig. 6. PDMS structuring results using laser setup No. 1 are summarized in Table 2.

Fig. 6 SEM micrograph of an array of 3D structures fabricated out of pure PDMS. The cumulative energy Eac=Epvs(2w0fr)Pavvs scales linearly with an average power Pav = Epfr. The best fabrication conditions (a fidelity of recovered 3D structures) scales linearly in presentation Pav vs. vs (this is more clearly appreciated in a log - log presentation) indicating a linear process of polymerization. Dashed lines mark good quality structures.

Table 2. PDMS structuring with different photo-initiators using laser setup No. 1 (λ = 515 nm, tp = 300 fs, fr = 200 kHz). PI numbering is kept from Table 1 with addition of 3-c corresponding to 0.2 % concentration of ISO which was not used previously.

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It was noticed that using the same fabrication parameters the quality of the structures was considerably worse when only the stages were used for sample translation as compared to the structures fabricated using stages combined with galvano-scanners (see, Fig. 7). Higher fabrication throughput was also achieved in the later case (vs = 1.5 mm/s, throughput of 180 μm3/s with pure PDMS and 0.2% wt THIO, and vs = 6 mm/s, throughput of 720 μm3/s with 0.5% wt ISO).

Fig. 7 (a – b) 3D structures fabricated using only linear translation stages for sample translation; (c – d) using stages combined with galvanometric scanners. (b) and (d) show magnified images of the structures, fabricated using the same parameters (Pav = 0.5 mW, Ip ≈ 1.20 TW/cm2, vs = 1.2 mm/s.)

It is noteworthy, the use of second harmonics makes perfect cancellation of the nanoseconds long pedestal of the fs-laser pulse which can affect ionization at the focus [38

38. S. Juodkazis, Y. Nishi, H. Misawa, V. Mizeikis, O. Schecker, R. Waitz, P. Leiderer, and E. Scheer, “Optical transmission and laser structuring of silicon membranes,” Opt. Express 17, 15308–15317 (2009) [CrossRef] [PubMed] .

]. Also, the wavelength λ = 515 nm is perfectly matching the two photon absorption conditions of the THIO and ISO which have direct absorption peak at approximately 360 nm = 0.7 × λ (see, Fig. 1) [39

39. M. Malinauskas, A. Žukauskas, G. Bičkauskaitė, R. Gadonas, and S. Juodkazis, “Mechanisms of three-dimensional structuring of photo-polymers by tightly focussed femtosecond laser pulses,” Opt. Express 18, 10209–10221 (2010) [CrossRef] [PubMed] .

]. The largest 2D and 3D throughput using the laser setup No. 1 were 1800 μm2/s and 720 μm3/s, respectively.

3.3. Mechanisms of polymerization

In practical applications very different laser fabrication conditions are used: wavelength, λ, pulse duration, τp, repetition rate, fr, peak irradiance, Ip (which is important for the nonlinear absorption and refraction), and the exposure dose or a number of overlapping pulses, Np. We present here generic estimations of electron generation rates, hence, bond breaking probability which facilitates a polymer cross linking. These order of magnitude estimations predict qualitatively well the thresholds of dielectric breakdown of SZ2080 resist with different photo-initiators and explain the mechanism of polymerization using fs- and ps-laser pulses [39

39. M. Malinauskas, A. Žukauskas, G. Bičkauskaitė, R. Gadonas, and S. Juodkazis, “Mechanisms of three-dimensional structuring of photo-polymers by tightly focussed femtosecond laser pulses,” Opt. Express 18, 10209–10221 (2010) [CrossRef] [PubMed] .

, 40

40. M. Malinauskas, P. Danilevicius, and S. Juodkazis, “Three-dimensional micro-/nano-structuring via direct write polymerization with picosecond laser pulses,” Opt. Express 19, 5602–5610 (2011) [CrossRef] [PubMed] .

].

The multi-photon absorption and avalanche rates of electron multiplication wmpi and wimp, respectively, are given by [41

41. E. G. Gamaly, Femtosecond Laser-Matter Interactions: Theory, Experiments and Applications (Pan Stanford Publishing, USA, 2011).

]:
wmpiwnph3/2(εosc2Ji)nph,
(1)
wimpεoscJi2ω2νeph(νeph2+ω2),
(2)
where nph = Jie/() + 1 is the number of photons required for direct absorption (truncated to an integer) with Ji being the ionization potential of material, h Plank’s constant, ω = 2πc/λ is the cyclic frequency of light of wavelength λ, e electron charge, and c speed of light. The electron quiver energy εosc=e2E24mω2 with the electrical field strength defined by intensity/irradiance, Ip, as E=Ip/(cε0n), where ε0 is the vacuum permittivity constant and n is the refractive index of the ambience (material). The electron ion interaction is governed by the electron-phonon momentum exchange rate, νeph.

With the multi-photon absorption and avalanche rates estimated by Eqns. 1 and 2, it is possible to calculate the rate of free electron generation, hence, the rate of free radical creation:
dnedt=newimp+nawmpi,
(3)
where ne is free electron density (available only for the avalanche multiplication) and na is the atom density (available only for the multi-photon ionization). Solution of Eqn. 3 is following:
ne(I,λ,t)=[ne0+nawmpiwimp[1ewimpt]]ewimpt
(4)
This equation allows to explicitly follow the ionization in time I(t) [42

42. S. Juodkazis, A. V. Rode, E. G. Gamaly, S. Matsuo, and H. Misawa, “Recording and reading of three-dimensional optical memory in glasses,” Appl. Phys. B 77, 361–368 (2003) [CrossRef] .

]; here ne0 is the initial (dark) electron density in material ∼ 1010 cm−3.

Let us evaluate the values of wmpi and wimp for the used polymerization of undoped PDMS which has a strong absorption at λg ≃ 225 nm or Ji = 5.5 eV (see, Fig. 1) considered here as the direct absorption transition. Then a 3-photon process is required nph = 3 at the laser fabrication wavelength λ = 515 nm for the free electron generation. For the typical pulse intensity Ip = 2.5 TW/cm2 used in 2/3D fabrication: wmpi = 1.5 ×108 s−1 and wimp = 4.7 ×1012 s−1, respectively, for the focusing inside PDMS; the refractive index n = 1.4 – 1.42 (according to the manufacturer) and electron quiver energy εosc = 4 meV. The value νeph ≃ 6 × 1014 s−1[39

39. M. Malinauskas, A. Žukauskas, G. Bičkauskaitė, R. Gadonas, and S. Juodkazis, “Mechanisms of three-dimensional structuring of photo-polymers by tightly focussed femtosecond laser pulses,” Opt. Express 18, 10209–10221 (2010) [CrossRef] [PubMed] .

] was not critically important for the estimation of mechanisms discussed here. Obviously, in the undoped PDMS wimpwmpi and this explains that sometimes a strong optical damage occurred during polymerization and a very high irradiance was required. If only a seeding of free electrons is provided from defect states and/or impurities in PDMS matrix, a strong avalanche makes a run away breakdown (see Table 1).

In the case of PDMS with ISO and THIO the absorption band exist at λg = 375 nm, Ji = 3.3 eV (see, Fig. 1). For the same Ip = 2.5 TW/cm2, one would find wmpi = 1.2 × 1011 s−1 and wimp = 7.8 × 1012 s−1 which are the rates on ionization of the photo-initiator molecules. Now, only nph = 2 is required for ionization of ISO and THIO and the two-photon absorption rate is only slightly smaller than the avalanche. The doping efficiently provides seeding electrons for ionization of the rest of PDMS matrix and allows to control overall ionization and free radical generation rate.

The estimations presented above are based on the peak intensity Ip = Ep/τp per pulse and the same values for τp = 300 fs (setup No. 1) and τp = 20 fs (setup No. 2) can be achieved at proportionally different pulse energies, Ep. Small Ep is beneficial for a precise control of the energy delivery and reduces chances of a run away breakdown. At the high repetition rate fr > 1 MHz, a thermal accumulation is important as we recently demonstrated [40

40. M. Malinauskas, P. Danilevicius, and S. Juodkazis, “Three-dimensional micro-/nano-structuring via direct write polymerization with picosecond laser pulses,” Opt. Express 19, 5602–5610 (2011) [CrossRef] [PubMed] .

]. The number of pulses overlapped per focal spot Np = 2w0/(vs/fr) in the case of the highest throughput fabrication was Np ≃ 17 for the spot size 2w0 = 1.22λ/NA, NA = 1.25, λ = 515 nm and scan velocity of vs = 6 mm/s. At the repetition rate fr = 75 MHz and short laser pulses of τp = 20 fs just a fs-oscillator is required to fabricate at the required irradiance and scanning velocities can be large making this a practical solution for applications. Indeed, for the same wavelength and focusing conditions, only Ep = 0.1 nJ is required for Ip ≃ 2.5 TW/cm2. When thermal accumulation is present, i.e., a temperature diffusion time over the spot size, 2w0, is larger than the temporal separation between pulses, 1/fr, at typically fr ≥ 0.5 MHz in glasses and polymers [40

40. M. Malinauskas, P. Danilevicius, and S. Juodkazis, “Three-dimensional micro-/nano-structuring via direct write polymerization with picosecond laser pulses,” Opt. Express 19, 5602–5610 (2011) [CrossRef] [PubMed] .

], the thermally driven polymerization becomes possible. However, energy delivery should be very precisely controlled to avoid a thermal run away breakdown of an inherently exothermic polymerization reaction.

In order to increase the fabrication throughput, dry objective lenses should be used since approximately at vs > 1 mm/s strong vibrations are introduced when immersion oil is mediating the objective lens contact with sample; this might be one of the reasons of the lower quality structures at the high velocities as recognizable in Fig. 7. High repetition fs-oscillators with short pulse duration of τp = 20 fs can prove beneficial to further improve the demonstrated throughput values. Since short fs-pulses are sensitive to chirp in dispersive media, the ionization rate at the focus can be additionally controlled by controlling the chirp of the pulse [43

43. K. Hatanaka, T. Ida, H. Ono, S.-I. Matsushima, H. Fukumura, S. Juodkazis, and H. Misawa, “Chirp effect in hard X-ray generation from liquid target when irradiated by femtosecond pulses,” Opt. Express 16, 12650–12657 (2008) [CrossRef] [PubMed] .

]. Also, a spatial chirp - the pulse front tilt - can be used to control polymerization as it was demonstrated for the dielectric breakdown [44

44. S. Juodkazis, K. Nishimura, and H. Misawa, “Three-dimensional laser structuring of materials at tight focusing,” Chin. Opt. Lett. 5, S198–200 (2007).

]. Combination of linear stage scan together with galvano scan in opposite directions would sum up the scanning velocities. The current state-of-the-art hardware typically used in fs-laser fabrication can deliver 10 cm/s speeds of the irradiation point on the samples’s surface. This technique can become attractive for medical applications, e.g., fabrication of complex 3D networks of blood vessels [12

12. P. Danilevicius, S. Rekstyte, E. Balciunas, A. Kraniauskas, R. Jarasiene, R. Sirmenis, D. Baltriukiene, V. Bukelskiene, R. Gadonas, and M. Malinauskas, “Micro-structured polymer scaffolds fabricated by direct laser writing for tissue engineering,” J. Biomed. Optics 17, 081405 (2012) [CrossRef] .

, 45

45. S. Juodkazis, “Writing 3D patterns of microvessels,” Int. J. Nanomed. 2012, 3701–3702 (2012) [CrossRef] .

]. By combination of linear and galvano scanners, it is possible to reach 720 μm3/s throughput using laser setup No. 1 with NA ∼ 1.25 focusing. Hence, a high spatial resolution of structuring and almost 300× higher throughput is achieved as compared to the current state-of-the-art in laser structuring of PDMS.

4. Conclusion

We have shown direct laser writing of 2D and 3D structures in PDMS elastomer with throughput of ∼ 720 μm3/s which is larger than that (∼ 12 μm3/s) reported previously [9

9. C. Coenjarts and C. Ober, “Two-photon three-dimensional microfabrication of poly(dimethylsiloxane) elastomers,” Chem. Mater. 16, 5556–5558 (2004) [CrossRef] .

, 10

10. T. Hasegawa, K. Oishi, and S. Maruo, “Three-dimensional microstructuring of PDMS by two-photon microstereolithography,” IEEE 06, 158–161 (2006).

]. Structuring with visible 515 nm wavelength, 300 fs pulses at 200 kHz and NA = 1.25 focusing, the achieved throughput was ∼ 720 μm3/s while at the near-IR wavelength of 800 nm, 20 fs, 75 MHz and NA = 1.4 the throughput was ∼ 20 μm3/s.

Photo-initiators ISO and THIO at 0.2–1% wt were required for the high fidelity fabrication in viscous liquid PDMS photo-polymer. These photo-initiators are not toxic and fabricated structures can be used for cell cultures [46

46. C. Williams, A. Malika, T. Kima, P. Mansonb, and J. Elisseeffa, “Variable cytocompatibility of six cell lines with photoinitiators used for polymerizing hydrogels and cell encapsulation,” Biomaterials 26, 12111218 (2005) [CrossRef] .

]. The 3D sculpturing at similar sample translation velocities with comparable average laser power were used in pure PDMS and with 0.2% wt THIO. Combination of stage and galvano-scanners allowed to achieve ∼ 6 mm/s fabrication velocities and is promising for the high-throughput applications such as fabrication of bio-scaffolds. Apparently, use of scanners was beneficial to create smoother surfaces of fabricated structures.

Acknowledgments

SR is grateful for support by FASTQUAST (PITN-GA-2008-214962) EU mobility grant and “BIOMATRIX” grant (No. 31V-43/2013) from the Agency for Science, Innovation and Technology. MM acknowledges financial support by MIKROŠVIESA research grant (No. MIP-12241) from the Research Council of Lithuania. SJ is grateful for partial support via Discovery grant DP120102980 from Australian Research Council. Authors would like to thank Dr. Maria Farsari for providing access to NonLinear Lithography laboratory (IESL-FORTH) and critical discussions; we thank Mrs. Aleka Manousaki for expert technical assistance with SEM.

References and links

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J. Lotters, W. Olthuis, P. Veltink, and P. Bergveld, “The mechanical properties of the rubber elastic polymer polydimethylsiloxane for sensor applications,” J. Micromech. Microeng. 7, 145–147 (2006) [CrossRef] .

2.

J. Lee, X. Jiang, D. Ryan, and G. Whitesides, “Compatibility of mammalian cells on surfaces of poly(dimethylsiloxane),” Langmuir 20, 11684–11691 (2004) [CrossRef] [PubMed] .

3.

T. Thorsen, S. Maerkl, and S. Quake, “Microfluidic large scale integration,” Science 298, 580–584 (2002) [CrossRef] [PubMed] .

4.

E. Leclerc, Y. Sakai, and T. Fujii, “Cell culture in 3-dimensional microfluidic structure of PDMS (polydimethylsiloxane),” Biomed. Microdev. 5, 109–114 (2003) [CrossRef] .

5.

N.-T. Nguyen, “Micro-optofluidic lenses: a review,” Biomicrofluidics 4, 031501 (2010) [CrossRef] [PubMed] .

6.

A. Werber and H. Zappe, “Tunable microfluidic microlenses,” Appl. Opt. 44, 3238–3245 (2005) [CrossRef] [PubMed] .

7.

J.-H. Jang, C. Ullal, T. Gorishnyy, V. Tsukruk, and E.L. Thomas, “Mechanically tunable three-dimensional elastomeric network/air structures via interference lithography,” Nano Lett. 6, 740–743 (2006) [CrossRef] [PubMed] .

8.

B. Gates, Q. Xu, J. Love, D. Wolfe, and G. Whitesides, “Unconventional nanofabrication,” Annu. Rev. Mater. Res. 34, 339–372 (2004) [CrossRef] .

9.

C. Coenjarts and C. Ober, “Two-photon three-dimensional microfabrication of poly(dimethylsiloxane) elastomers,” Chem. Mater. 16, 5556–5558 (2004) [CrossRef] .

10.

T. Hasegawa, K. Oishi, and S. Maruo, “Three-dimensional microstructuring of PDMS by two-photon microstereolithography,” IEEE 06, 158–161 (2006).

11.

H. Selvaraj, B. Tan, and K. Venkatakrishnan, “Maskless direct micro-structuring of pdms by femtosecond laser localized rapid curing,” J. Micromech. Microeng. 21, 075018 (2011) [CrossRef] .

12.

P. Danilevicius, S. Rekstyte, E. Balciunas, A. Kraniauskas, R. Jarasiene, R. Sirmenis, D. Baltriukiene, V. Bukelskiene, R. Gadonas, and M. Malinauskas, “Micro-structured polymer scaffolds fabricated by direct laser writing for tissue engineering,” J. Biomed. Optics 17, 081405 (2012) [CrossRef] .

13.

M. Malinauskas, A. Zukauskas, V. Purlys, K. Belazaras, A. Momot, D. Paipulas, R. Gadonas, A. Piskarskas, H. Gilbergs, A. Gaidukeviciute, I. Sakellari, M. Farsari, and S. Juodkazis, “Femtosecond laser polymerization of hybrid/integrated micro-optical elements and their characterization,” J. Opt. 12, 124010 (2010) [CrossRef] .

14.

A. Ovsianikov, M. Malinauskas, S. Schlie, B. Chichkov, S. Gittard, R. Narayan, M. Löbler, K. Sternberg, K.-P. Schmitz, and A. Haverich, “Three-dimensional laser micro- and nano-structuring of acrylated poly(ethylene glycol) materials and evaluation of their cytoxicity for tissue engineering applications,” Acta Biomater. 7, 967–974 (2011) [CrossRef] .

15.

S. Turunen, E. Kapyla, K. Terzaki, J. Viitanen, C. Fotakis, M. Kellomaki, and M. Farsari, “Pico- and femtosecond laser-induced crosslinking of protein microstructures: evaluation of processability and bioactivity,” Biofabrication p. 045002 (2011) [CrossRef] [PubMed] .

16.

M. Malinauskas, G. Kiršanskė, S. Rekštytė, T. Jonavičius, E. Kaziulionytė, L. Jonušauskas, A. Žukauskas, R. Gadonas, and A. Piskarskas, “Nanophotonic lithography: A versatile tool for manufacturing functional three-dimensional micro-/nano-objects,” Lith. J. Phys. 52, 312–326 (2012) [CrossRef] .

17.

G. von Freymann, A. Ledermann, M. Thiel, I. Staude, S. Essig, K. Busch, and M. Wegener, “Three-dimensional nanostructures for photonics,” Adv. Funct. Mater. 20, 1038–1052 (2010) [CrossRef] .

18.

J. Trull, L. Maigyte, V. Mizeikis, M. Malinauskas, S. Juodkazis, C. Cojocaru, M. Rutkauskas, M. Peckus, V. Sirutkaitis, and K. Staliunas, “Formation of collimated beams behind the woodpile photonic crystal,” Phys. Rev. A 84, 033812 (2011) [CrossRef] .

19.

E. Brasselet, M. Malinauskas, A. Žukauskas, and S. Juodkazis, “Photopolymerized microscopic vortex beam generators: precise delivery of optical orbital angular momentum,” Appl. Phys. Let. 97, 211108 (2010) [CrossRef] .

20.

S. Maruo, K. Ikuta, and H. Korogi, “Force-controllable, optically driven micromachines fabricated by single-step two-photon microstereolithography,” J. Microelectromechanic. Syst. 12, 533–539 (2003) [CrossRef] .

21.

C. Schizas, V. Melissinaki, A. Gaidukeviciute, C. Reinhardt, C. Ohrt, V. Dedoussis, B. Chichkov, C. Fotakis, M. Farsari, and D. Karalekas, “On the design and fabrication by two-photon polymerization of a readily assembled micro-valve,” Int. J. Adv. Manuf. Technol. 48, 435–441 (2010) [CrossRef] .

22.

Y.-L. Zhang, Q.-D. Chen, H. Xia, and H.-B. Sun, “Designable 3D nanofabrication by femtosecond laser direct writing,” Nano Today 5, 435–448 (2010) [CrossRef] .

23.

D. Lipomi, R. Martinez, L. Cademartiri, and G. Whitesides, “Soft lithographic approaches to nanofabrication,” Polymer Sci. 7, 211–231 (2012).

24.

C. LaFratta, L. Li, and J. Fourkas, “Soft-lithographic replication of 3d microstructures with closed loops,” PNAS 103, 8589–8594 (2006) [CrossRef] [PubMed] .

25.

P. Danilevicius, S. Rekstyte, E. Balciunas, A. Kraniauskas, R. Sirmenis, D. Baltriukiene, V. Bukelskiene, R. Gadonas, V. Sirvydis, A. Piskarskas, and M. Malinauskas, “Laser 3D micro/nanofabrication of polymers for tissue engineering applications,” Opt. Laser Technol. 45, 518–524 (2013) [CrossRef] .

26.

E. Gamaly, S. Juodkazis, V. Mizeikis, H. Misawa, A. Rode, and W. Krolokowski, “Modification of refractive index by a single fs-pulse confined inside a bulk of a photo-refractive crystal,” Phys. Rev. B 81, 054113 (2010) [CrossRef] .

27.

S. Juodkazis, K. Nishimura, S. Tanaka, H. Misawa, E. E. Gamaly, B. Luther-Davies, L. Hallo, P. Nicolai, and V. Tikhonchuk, “Laser-induced microexplosion confined in the bulk of a sapphire crystal: Evidence of multi-megabar pressures,” Phys. Rev. Lett. 96, 166101 (2006) [CrossRef] [PubMed] .

28.

E. E. Gamaly, S. Juodkazis, K. Nishimura, H. Misawa, B. Luther-Davies, L. Hallo, P. Nicolai, and V. Tikhonchuk, “Laser-matter interaction in a bulk of a transparent solid: confined micro-explosion and void formation,” Phys. Rev. B 73, 214101 (2006) [CrossRef] .

29.

M. Malinauskas, V. Purlys, M. Rutkauskas, A. Gaidukevičiutė, and R. Gadonas, “Femtosecond visible light induced two-photon photopolymerization for 3D micro/nanostructuring in photoresists and photopolymers,” Lith. J. Phys. 50, 201–208 (2010) [CrossRef] .

30.

F. Claeyssens, E. A. Hasan, A. Gaidukevičiūtė, D. S. Achilleos, A. Ranella, C. Reinhardt, A. Ovsianikov, X. Shizhou, C. Fotakis, M. Vamvakaki, B. N. Chichkov, and M. Farsari, “Production of biodegradable tissue engineering scaffold materials via 2-photon polymerisation,” Langmuir 25, 3219–3223 (2009) [CrossRef] [PubMed] .

31.

3DPoli@gmail.com.

32.

M. Malinauskas, G. Bičkauskaitė, M. Rutkauskas, D. Paipulas, V. Purlys, and R. Gadonas, “Self-polymerization of nano-fibres and nano-membranes induced by two-photon absorption,” Lith. J. Phys. 50, 135–140 (2010) [CrossRef] .

33.

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

34.

Y. Li, H. Cui, F. Qi, H. Yang, and Q. Gong, “Uniform suspended nanorods fabricated by bidirectional scanning via two-photon photopolymerization,” Nanotechnology 19, 375304 (2008) [CrossRef] [PubMed] .

35.

K. Takada, D. Wu, Q.-D. Chen, S. Shoji, H. Xia, S. Kawata, and H.-B. Sun, “Size-dependent behaviors of femtosecond laser-prototyped polymer micronanowires,” Opt. Lett. 34, 566–568 (2009) [CrossRef] [PubMed] .

36.

S. Juodkazis, V. Mizeikis, S. Matsuo, K. Ueno, and H. Misawa, “Three-dimensional micro- and nano-structuring of materials by tightly focused laser radiation,” Bull. Chem. Soc. Jpn. 81, 411–448 (2008) [CrossRef] .

37.

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] .

38.

S. Juodkazis, Y. Nishi, H. Misawa, V. Mizeikis, O. Schecker, R. Waitz, P. Leiderer, and E. Scheer, “Optical transmission and laser structuring of silicon membranes,” Opt. Express 17, 15308–15317 (2009) [CrossRef] [PubMed] .

39.

M. Malinauskas, A. Žukauskas, G. Bičkauskaitė, R. Gadonas, and S. Juodkazis, “Mechanisms of three-dimensional structuring of photo-polymers by tightly focussed femtosecond laser pulses,” Opt. Express 18, 10209–10221 (2010) [CrossRef] [PubMed] .

40.

M. Malinauskas, P. Danilevicius, and S. Juodkazis, “Three-dimensional micro-/nano-structuring via direct write polymerization with picosecond laser pulses,” Opt. Express 19, 5602–5610 (2011) [CrossRef] [PubMed] .

41.

E. G. Gamaly, Femtosecond Laser-Matter Interactions: Theory, Experiments and Applications (Pan Stanford Publishing, USA, 2011).

42.

S. Juodkazis, A. V. Rode, E. G. Gamaly, S. Matsuo, and H. Misawa, “Recording and reading of three-dimensional optical memory in glasses,” Appl. Phys. B 77, 361–368 (2003) [CrossRef] .

43.

K. Hatanaka, T. Ida, H. Ono, S.-I. Matsushima, H. Fukumura, S. Juodkazis, and H. Misawa, “Chirp effect in hard X-ray generation from liquid target when irradiated by femtosecond pulses,” Opt. Express 16, 12650–12657 (2008) [CrossRef] [PubMed] .

44.

S. Juodkazis, K. Nishimura, and H. Misawa, “Three-dimensional laser structuring of materials at tight focusing,” Chin. Opt. Lett. 5, S198–200 (2007).

45.

S. Juodkazis, “Writing 3D patterns of microvessels,” Int. J. Nanomed. 2012, 3701–3702 (2012) [CrossRef] .

46.

C. Williams, A. Malika, T. Kima, P. Mansonb, and J. Elisseeffa, “Variable cytocompatibility of six cell lines with photoinitiators used for polymerizing hydrogels and cell encapsulation,” Biomaterials 26, 12111218 (2005) [CrossRef] .

OCIS Codes
(140.3390) Lasers and laser optics : Laser materials processing
(220.4000) Optical design and fabrication : Microstructure fabrication
(350.3850) Other areas of optics : Materials processing
(160.1245) Materials : Artificially engineered materials

ToC Category:
Laser Microfabrication

History
Original Manuscript: March 18, 2013
Revised Manuscript: May 24, 2013
Manuscript Accepted: May 30, 2013
Published: July 10, 2013

Virtual Issues
Vol. 8, Iss. 8 Virtual Journal for Biomedical Optics

Citation
Sima Rekštytė, Mangirdas Malinauskas, and Saulius Juodkazis, "Three-dimensional laser micro-sculpturing of silicone: towards bio-compatible scaffolds," Opt. Express 21, 17028-17041 (2013)
http://www.opticsinfobase.org/vjbo/abstract.cfm?URI=oe-21-14-17028


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References

  1. J. Lotters, W. Olthuis, P. Veltink, and P. Bergveld, “The mechanical properties of the rubber elastic polymer polydimethylsiloxane for sensor applications,” J. Micromech. Microeng.7, 145–147 (2006). [CrossRef]
  2. J. Lee, X. Jiang, D. Ryan, and G. Whitesides, “Compatibility of mammalian cells on surfaces of poly(dimethylsiloxane),” Langmuir20, 11684–11691 (2004). [CrossRef] [PubMed]
  3. T. Thorsen, S. Maerkl, and S. Quake, “Microfluidic large scale integration,” Science298, 580–584 (2002). [CrossRef] [PubMed]
  4. E. Leclerc, Y. Sakai, and T. Fujii, “Cell culture in 3-dimensional microfluidic structure of PDMS (polydimethylsiloxane),” Biomed. Microdev.5, 109–114 (2003). [CrossRef]
  5. N.-T. Nguyen, “Micro-optofluidic lenses: a review,” Biomicrofluidics4, 031501 (2010). [CrossRef] [PubMed]
  6. A. Werber and H. Zappe, “Tunable microfluidic microlenses,” Appl. Opt.44, 3238–3245 (2005). [CrossRef] [PubMed]
  7. J.-H. Jang, C. Ullal, T. Gorishnyy, V. Tsukruk, and E.L. Thomas, “Mechanically tunable three-dimensional elastomeric network/air structures via interference lithography,” Nano Lett.6, 740–743 (2006). [CrossRef] [PubMed]
  8. B. Gates, Q. Xu, J. Love, D. Wolfe, and G. Whitesides, “Unconventional nanofabrication,” Annu. Rev. Mater. Res.34, 339–372 (2004). [CrossRef]
  9. C. Coenjarts and C. Ober, “Two-photon three-dimensional microfabrication of poly(dimethylsiloxane) elastomers,” Chem. Mater.16, 5556–5558 (2004). [CrossRef]
  10. T. Hasegawa, K. Oishi, and S. Maruo, “Three-dimensional microstructuring of PDMS by two-photon microstereolithography,” IEEE06, 158–161 (2006).
  11. H. Selvaraj, B. Tan, and K. Venkatakrishnan, “Maskless direct micro-structuring of pdms by femtosecond laser localized rapid curing,” J. Micromech. Microeng.21, 075018 (2011). [CrossRef]
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