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Laser-Induced Periodic Surface Structures (LIPSS) on Polymer Surfaces

Johannes Heitza,*, Bettina Reisingera, Marc Fahrnerb, Christoph Romaninb, Jakub Siegelc, Vaclav Svorcikc a, * Institute of Applied Physics, Johannes Kepler University Linz, Altenbergerstr. 69, 4040 Linz, Austria b Institute of Biophysics, Johannes Kepler University Linz, Altenbergerstr. 69, 4040 Linz, Austria c Department of Solid State Engineering, Institute of Chemical Technology Prague, Technicka 5, 166 28 Prague 6, Czech Republic Tel: (43)732 24689248, Fax: (43)732 24689248, e-mail: johannes.heitz@jku.at ABSTRACT Frequently observed structures in laser-surface processing are ripples, also denoted as laser-induced periodic surface structures (LIPSS). Ripples originate from the interference of the incident/refracted laser light with the scattered or diffracted light near the surface. For many polymer surfaces, organized nano-ripple structures surfaces can be induced by irradiation with pulsed UV lasers with pulse lengths in the order of some nanoseconds at fluences well below the ablation threshold and with a large number of laser pulses N. After exposure to linearly polarized radiation at normal incidence, the lateral period of the observed LIPSS is close to the wavelength . This type of structures is usually called low spatial frequency LIPSS (LSFL). For femto-second laser light, ripples at polymer surfaces are also observed at a laser fluence above the ablation threshold, even with low numbers of laser pulses N. Under special conditions, another type of ripples with periods as small as /3 has been reported. This type of ripples is called high spatial frequency LIPSS (HSFL). We summarize here our work on LIPSS generation at polymers and describe potential applications in the field of self-organized formation of gold nano-wires and nano-structure induced alignment of biological cells cultivated on polymer substrates. Keywords: laser-induced nanostructures, polymer surfaces, ripples, gold nano-structures, biological cells. 1. INTRODUCTION Periodic variations in the refractive index are frequently used for photonic devices, such as Bragg mirrors, holographic gratings, photonic crystal waveguides, photonic crystal fibers, or imprinted holograms. For light coupling often the first order diffraction from a periodic structure is used. Reported examples are for instance the in-coupling of light into plasmonic structures at surfaces or the out-coupling of light from a quantum cascade laser. A similar effect can also be exploited for production of photonic nano-structures. I.e., the interference of an incident laser beam with first order diffracted light running parallel to a surface can induce the formation of periodic ripple structures, which are frequently observed in laser-surface processing [1]. These are spatially periodic structures, also denoted as laser-induced periodic surface structures (LIPSS). Ripple formation was first observed by Birnbaum (1965) after ruby-laser irradiation of various semiconductor surfaces [2]. Further investigations have shown that ripple formation is a quite general phenomenon, which is practically always observed on solid or liquid surfaces after laser irradiation with polarized light within certain ranges of laser parameters. Ripples originate from the interference of the incident/refracted laser light with the scattered or diffracted light near the surface, but the precise physical mechanism and their occurrence depend on the material and the irradiation parameters. Particularly the work of Sipe et al. represents a first-principle theory which takes into consideration the interaction of an electromagnetic wave with a microscopically rough surface, which also includes the excitation of surface polaritons [3]. For femto-second laser light, ripples are frequently observed at a laser fluence, , above the ablation threshold [4, 5, 6], even with low numbers of laser pulses N. In many materials such as metals and semiconductors, after exposure to linearly polarized radiation at normal incidence, the lateral period of the observed LIPSS is very close to the wavelength of the incident radiation. This type of structures is usually called low spatial frequency LIPSS (LSFL). In recent studies of femto-second laser irradiation of various solids, another type of sub-wavelength ripples with periods as small as /3 has been reported at fluence levels typically below the single-pulse ablation threshold. This distinct type of ripples is called high spatial frequency LIPSS (HSFL). The nature of those sub-wavelength HSFL is still quite controversially discussed in literature and very different mechanisms have been proposed such as interference effects along with transient changes in the optical properties during laser irradiation, laser-induced changes in the complex refractive index due to generation of quasi-free electrons in the conduction band or due to the Kerr effect, second harmonic generation (SHG), excitation of surface plasmon polaritons, self-organization, or chemical changes in the laser-affected surface [7]. In the present paper, we show that such photonic nano-structures at polymer surfaces may have applications for formation of gold nano-structures or for cell biology.

978-1-4673-2229-4/12/$31.00 2012 IEEE

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2. RIPPLES AT POLYMER SURFACES For many polymer surfaces (including polyethylene terephthalate (PET), polyimide (PI), and polystyrene (PS)), organized LSFL nano-ripple structures surfaces can be induced by irradiation with pulsed UV lasers with laser pulse lengths in the order of some nano-seconds at fluences well below the ablation threshold and with a large number of laser pulses (typically about 5000). It was found that the periodicity and the height of the structures depend on the laser wavelength, , as well as the angle of incidence, , of the laser beam [8, 9, 10]. For spolarization, the lateral periodicity is given by
=

n eff sin

(1)

The minimum value of can be calculated by the laser wavelength divided by the effective index of refraction neff , which lies between the refractive index of air ( 1) and the refractive index of the polymer (typically 1.5). The direction of the ripples on PET is parallel to the direction of polarization. This orientation is typical for polymers, while ripples for most other materials (i.e., metals and semi-conductors) have an orientation perpendicular to the polarization. The smallest features of this kind reported so far were produced by our group by 157 nm F2 excimer laser irradiation of PET foils [11]. Examples for such structures are shown in Fig. 1. The period of the ripples depends on the laser wavelength and on the angle of incidence of the radiation, according formula (1).
(a) (b) (c)

Figure 1. LSFL-type ripples on polymer surfaces induced by nano-second laser irradiation: AFM images of = 157 nm F2 induced ripples at PET irradiated under angle of (a) 0, (b) 22.5, and (c) 45. Ripple period is about 140 nm, 195 nm, and 280 nm and ripple height about 30 nm, 50 nm, and 95 nm, respectively [11]. Only few groups have studied the femto-second laser induced ripple generation on polymer surfaces [12]. At fluences below the ablation threshold and multi-pulse exposure, the formation of LSFL structures has been reported, which were similar to those obtained with nano-second lasers with comparable wavelengths [13]. In the case of 800 nm femto-second laser irradiation of PI foils at fluences above the ablation threshold, LSFL ripples have been observed parallel to the electric field of the laser light with a period comparable to [14]. In a recent publication of the same group, the authors report that the parallel orientation of the ripple direction to the electrical field was obtained only for pulse numbers N > 5, while ripples produced with lower pulse numbers were independently oriented [15]. In the case of a resonant one-photon excitation with 248 nm, also ripples with a perpendicular orientation to the polarization and/or considerably smaller periodicity than were observed [16], as is shown exemplarily in Fig. 2 for 500 fs 248 nm KrF* excimer-laser irradiation of the polymers PI and PET under normal incidence. Probably, these structures are similar to HSFL ripples observed recently for other materials, whose formation mechanisms are however not understood as discussed before. Also, the reason for the different orientations of the ripples versus the polarization is not clear yet.

Figure 2. HSFL-type ripples on polymer surfaces induced by femto-second laser irradiation: electron microscope images of surface structures on (a) PI irradiated with a 500 fs 248 nm KrF* excimer laser beam at a fluence = 14 mJ/cm2 and N = 60 laser pulses and (b) PET with = 79 mJ/cm2 and N = 5. The arrows P indicate the direction of the laser light polarization [16].

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3. GOLD NANO-STRUCTURES In our previous work [11], we demonstrated that laser-induced nano-structures on polymer surfaces can be used self-organized formation of gold nano-wires. Gold nano-layers were deposited onto KrF* laser irradiated PET surfaces with coherent ripples patterns with a lateral periodicity in the order of the wavelength of the laser light and with a corrugation height of several 10 nm. The deposited layers were then prepared by sputtering. This led to the formation of separated nano-wires at the ridges of the nano-patterns and not to a continuous metal layer, as we obtained in case of gold evaporation. As demonstrated in Fig. 3, the separation between the individual nano-wires was most pronounce3d if the sputtering was performed under grazing incidence.

Figure 3. Separated gold nano-wires on laser-induced ripples: electron microscope image of focussed ion-beam cutted PET sample with KrF* laser-induced HSFL-type ripples sputted with gold under grazing incidence. 4. BIOLOGICAL CELLS The nano-scale topography of biomaterial surfaces is important for many potential applications in medicine and biotechnology as they strongly influence cell function, adhesion and proliferation. Of special interest are polymer materials, because they are frequently used as cell culture dishes or for medical implants or prostheses. In a previous work, we showed that periodic surface structures generated by linearly polarized KrF* laser light (248 nm) on polystyrene (PS) foils can result in an alignment of living biological cells cultured thereon along the direction of the structures. The results indicate that the presence of nanostructures on the substrates can guide cell alignment along definite directions. The alignment depends on the type of cells and is only observed when the periodicity is above a critical periodicity value that is cell-type specific [9]. As a technology demonstrator, we now produced on commercially available polystyrene Petri dishes (SPL Life Sciences, Korea) laser-induced nano-ripples and used them to culture CHO cells (from a standard immortal cell line). Figure 4 shows the nanostructures on the surface of the polystyrene Petri dish and a phase contrast microscope image of the cells after one day of cell culture. The cells show a high degree of alignment from the beginning and after only two days they form a confluent monolayer. This proves clearly that the laser-processed substrate is very well suited for cell culture and that the nano-structures influence the cell shape.

Figure 4. Electron microscope images of nano-ripples on commercial Petri dish (left) and phase contrast microscope image of aligned CHO cells after 24 h in culture on commercial Petri-dish with laser-induced nanoripples (right). 5. CONCLUSIONS Laser-induced ripple formation is a method for large area nano-patterning of polymer surfaces with quasiperiodic line pattern. Ripple formation requires polarized laser light. For UV lasers with nano-second pulse lengths, the minimal lateral periodicity is obtained for perpendicular incidence and is slightly smaller than the laser-wavelength employed for production. The line orientation of the ripples is parallel to the polarization of the

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laser light. For inclined irradiation, the periodicity increases systematically with increasing angle of incidence. While ripple formation with nano-second lasers requires typically several thousand laser pulses and laser fluences below the ablation threshold, femto-second laser irradiation can result in ripple formation with only a few pulses at fluence above the ablation threshold. Under certain conditions, the periodicity of femto-second laser-induced ripples on polymers can be considerably smaller than the laser wavelength. The nano-patterned polymer surfaces are of interest for various fields of application, including self-organization of sputtered gold coatings and interaction with biological cells. ACKNOWLEDGEMENTS B.R acknowledges the financial support by the "JKU goes Gender" program. REFERENCES [1] D. Buerle: Laser Processing and Chemistry, Fourth Edition, Heidelberg: Springer-Verlag, 2011. [2] M. Birbbaum: Semiconductor surface damage produced by ruby lasers, J. Appl. Phys., vol. 36. pp. 36883698 ,1965. [3] J.E. Sipe, J.F. Preston, H.M. van Driel: Laser-induced periodic surface structure. I. Theory, Phys. Rev. B, vol. 27. pp. 1141-1154, 1983. [4] J. Bonse, A. Rosenfeld, J. Krger: Implications of transient changes of optical and surface properties of solids during femtosecond laser pulse irradiation to the formation of laser-induced periodic surface structures, Appl. Surf. Sci., vol. 257. pp. 5420-5423 , Apr. 2011. [5] F. Costache, S. Kouteva-Arguirova, J. Reif: Sub-damage-threshold femtosecond laser ablation from crystalline Si: surface nanostructures and phase transformation, Appl. Phys. A, vol. 79. pp. 1429-1432, Sep. 2004. [6] Y. Yang, J. Yang, L. Xue, Y. Guo: Surface patterning on periodicity of femtosecond laser-induced ripples, Appl. Phys. Lett., vol. 97, paper 141101, Oct. 2010. [7] D. Dufft, A. Rosenfeld, S. K. Das, R. Grunwald, J. Bonse: Femtosecond laser-induced periodic surface structures revisited: A comparative study on ZnO, J. Appl. Phys., vol. 105. paper 034908, Feb. 2009. [8] D. Buerle, E. Arenholz, V. Svorcik, J. Heitz, B. Lukyanchuk, N. Bityurin: Laser-induced surface modifications, structure formations, and ablation of organic polymers, Proc. SPIE, vol. 2403. pp. 312-320, 1995. [9] E. Rebollar, I. Frischauf, M. Olbrich, T. Peterbauer, S. Hering, J. Preiner, P. Hinterdorfer, C. Romanin, J. Heitz: Proliferation of aligned mammalian cells on laser-nanostructured polystyrene, Biomaterials, vol. 29, pp. 1796- 1806, Apr. 2008. [10] E. Rebollar, S. Perez, J.J. Hernandez, I. Martin-Fabiani, D.R. Rueda, T.A. Ezquerra, M. Castillejo: Assessment and formation mechanism of laser-induced periodic surface structures on polymer spin-coated films in real and reciprocal space, Langmuir, vol. 27, pp. 5596-5606, May 2011. [11] J. Siegel, P. Slepicka, J. Heitz, Z. Kolska, P. Sajdl, V. Svorcik: Gold nano-wires and nano-layers at laserinduced nano-ripples on PET, Appl. Surf. Sci., vol. 256. pp. 2205-2209, Jan. 2010. [12] T. Lippert, J.T. Dickinson: Chemical and spectroscopic aspects of polymer ablation: Special features and novel directions, Chem. Rev., vol. 103. pp. 453-485, Feb. 2003. [13] E. Rebollar, S. Perez, I. Martn-Fabiani, J.R. Vazquez De Aldana, D.R. Rueda, P. Moreno, T.A. Ezquerra, M. Castillejo: Laser induced periodic surface structuring of polymers and biopolymers: Formation mechanisms and assessment in real and reciprocal space, in Abstract Book COLA11, Cancun, Mexico, Nov. 2011, paper OTU-71. [14] S. Baudach, J. Bonse, W. Kautek: Ablation experiments on polyimide with femtosecond laser pulses, Appl. Phys. A, vol. 69, pp. S395S398, Dec. 1999. [15] M. Forster, W. Kautek, N. Faure, E. Audouard, R. Stoian: Periodic nanoscale structures on polyimide surfaces generated by temporally tailored femtosecond laser pulses, Phys. Chem. Chem. Phys., vol. 13. 4155-4158, 2011. [16] J. Heitz, E. Arenholz, D. Buerle, R. Sauerbrey, H. M. Phillips: Femtosecond excimer laser induced structure formation on polymers, Appl. Phys. A, vol. 59. pp. 289-293, Sep. 1994.