Esther Rebollar

Assessment and formation mechanism of laser-induced periodic surface structures on polymer spin-coated films in real and reciprocal space.

In this work we evaluate the potential of grazing incidence X-ray scattering techniques in the investigation of laser-induced periodic surface structures (LIPSSs) in a series of strongly absorbing model spin-coated polymer films which are amorphous, such as poly(ethylene terephthalate), poly(trimethylene terephthalate), and poly(carbonate bisphenol A), and in a weaker absorbing polymer, such as semicrystalline poly(vinylidene fluoride), over a narrow range of fluences. Irradiation was performed with pulses of 6 ns at 266 nm, and LIPSSs with period lengths similar to the laser wavelength and parallel to the laser polarization direction are formed by devitrification of the film surface at temperatures above the characteristic glass transition temperature of the polymers. No crystallization of the surface is induced by laser irradiation, and crystallinity of the material prevents LIPSS formation. The structural information obtained by both atomic force microscopy and grazing incidence small-angle X-ray scattering (GISAXS) correlates satisfactorily. Comparison of experimental and simulated GISAXS patterns suggests that LIPSSs can be well described considering a quasi-one-dimensional paracrystalline lattice and that irradiation parameters have an influence on the order of such a lattice.

Assessment of femtosecond laser induced periodic surface structures on polymer films

In this work we present the formation of laser induced periodic surface structures (LIPSS) on spin-coated thin films of several model aromatic polymers including poly(ethylene terephthalate), poly(trimethylene terephthalate) and poly carbonate bis-phenol A upon irradiation with femtosecond pulses of 795 and 265 nm at fluences well below the ablation threshold. LIPSS are formed with period lengths similar to the laser wavelength and parallel to the direction of the laser polarization vector. Formation of LIPSS upon IR irradiation at 795 nm, a wavelength at which the polymers absorb weakly, contrasts with the absence of LIPSS in this spectral range upon irradiation with nanosecond pulses. Real and reciprocal space characterization of LIPSS obtained by Atomic Force Microscopy (AFM) and Grazing Incidence Small Angle X-ray Scattering (GISAXS), respectively, yields well correlated morphological information. Comparison of experimental and simulated GISAXS patterns suggests that LIPSS can be suitably described considering a quasi-one-dimensional paracrystalline lattice and that irradiation parameters have an influence on the order of such a lattice. Fluorescence measurements, after laser irradiation, provide indirect information about dynamics and structure of the polymer at the molecular level. Our results indicate that the LIPSS are formed by interference of the incident and surface scattered waves. As a result of this process, heating of the polymer surface above its glass transition temperature takes place enabling LIPSS formation.

Grazing-incidence small-angle X-ray scattering of soft and hard nanofabricated gratings

Grazing-incidence small-angle X-ray scattering (GISAXS) has been used to structurally characterize model hard and soft gratings of nanotechnological interest. The different gratings exhibit GISAXS patterns with characteristic features that can be associated with their level of order along the direction of periodicity and the length of the lines. Highly ordered gratings, made out of silicon by electron beam lithography, and those nanofabricated on spin-coated polymer films by nanoimprint lithography, exhibit characteristic semicircle-like GISAXS patterns with intensity spots periodically distributed on a semicircle whose radius is related to the incidence angle used. These gratings can be considered as one-dimensional crystalline lattices as provided by computer simulations. Less ordered polymer gratings prepared by the laser-induced periodic surface structuring method exhibit a GISAXS pattern characterized by periodic rod-like scattering maxima whose intensity decreases with increasing horizontal scattering angle. In this case the gratings can be considered as one-dimensional paracrystals. The transition from a rod-like to a semicircle-like GISAXS pattern has been simulated and attributed to the contribution of the form factor by changing the length of the line (ripple). A critical length value for the transition is located at around a few micrometres.

Ultraviolet and infrared femtosecond laser induced periodic surface structures on thin polymer films

This work demonstrates the formation of femtosecond laser induced periodic surface structures (LIPSS) by multipulse irradiation with the fundamental and 3rd harmonic of a linearly polarized Ti:sapphire laser (795 and 265 nm) on thin films of the polymers poly (ethylene terephthalate), poly (trimethylene terephthalate), and poly (carbonate bisphenol A) prepared by spin-coating. LIPSS, inspected by atomic force microscopy, are formed upon multiple pulse UV and IR irradiation with wavelength-sized period in a narrow range of fluences below the ablation threshold. Control and tunability of the size and morphology of the periodic structures become thus possible ensuring photochemical integrity of polymer films.

Laser-induced periodic surface structures nanofabricated on poly(trimethylene terephthalate) spin-coated films.

Here we present a precise morphological description of laser-induced periodic surface structures (LIPSS) nanofabricated on spin-coated poly(trimethylene terephthalate) (PTT) films by irradiation with 266 nm, 6 ns laser pulses and by using a broad range of fluences and number of pulses. By accomplishing real and reciprocal space measurements by means of atomic force microscopy and grazing incidence wide- and small-angle X-ray scattering respectively on LIPSS samples, the range of optimum structural order has been established. For a given fluence, an increase in the number of pulses tends to improve LIPSS in PTT. However, as the pulse doses increase above a certain limit, a distortion of the structures is observed and a droplet-like morphology appears. It is proposed that this effect could be related to a plausible decrease of the molecular weight of PTT due to laser-induced chain photo-oxidation by irradiation with a high number of pulses. A concurrent decrease in viscosity enables destabilization of LIPSS by the formation of droplets in a process similar to surface-limited dewetting.

Dependence of ultraviolet nanosecond laser polymer ablation on polymer molecular weight: Poly(methyl methacrylate) at 248nm

We rely on a methodology demonstrated previously for assessing the temperature evolution and polymer viscosity changes in the 248nm irradiation of poly(methyl methacrylate)s (PMMAs) with molecular weights (Mw) ranging from 2.5to996kDa. Briefly, this methodology [G. Bounos et al., J. Appl. Phys. 98, 084317 (2005)] relies on monitoring the formation of aryl products in the irradiation of polymer doped with iodonaphthalene or iodophenanthrene. The results demonstrate that higher temperatures are attained with increasing Mw. The surface temperatures at the corresponding ablation thresholds are estimated to be ∼850–900K for Mw⩾120kDa vs ∼600K for 2.5kDa PMMA. In addition, for all Mw’s, melting is demonstrated (viscosity values of ≈101Pas), but it lasts longer for high Mw PMMAs. We ascribe these differences to the fact that low Mw PMMAs dissociate efficiently to desorbing monomers/oligomers, thereby resulting in more efficient energy removal. Even so, the ablation threshold of the high Mw PMMAs is attained at h...

Wavelength and pulse duration effects on laser induced changes on raw pigments used in paintings

In this study, the reaction of widely used artists pigments in raw form to pulsed laser radiation of different wavelengths and pulse duration was investigated. Vermilion, lead chromate and malachite (in the form of pellets) were irradiated using laser pulses of 500 fs at 248 nm, and pulses of 150 ps and 15 ns at 1064 and 213 nm. Optical microscopy, colorimetry, spectrofluorimetry, micro-Raman spectroscopy and X-ray photoelectron spectroscopy were employed to characterize the physicochemical changes induced to the pigments. Change of crystalline phase was identified for vermilion while reduction processes take place for lead chromate and malachite. It was found that these effects were minimized by application of ultraviolet ultrashort pulses (of femtosecond and picosecond duration) as compared with changes occurring by pulsed infrared irradiation (of both picosecond and nanosecond duration). The results presented are discussed in relation to previous research on painted mock-ups in order to elucidate the role and significance of the binding media in the laser induced discoloration of painted surfaces and thus to propose optimum laser cleaning practices.

Room temperature in-plane ⟨100⟩ magnetic easy axis for Fe3O4/SrTiO3(001):Nb grown by infrared pulsed laser deposition

We examine the magnetic easy-axis directions of stoichiometric magnetite films grown on SrTiO{sub 3}:Nb by infrared pulsed-laser deposition. Spin-polarized low-energy electron microscopy reveals that the individual magnetic domains are magnetized along the in-plane 〈100〉 film directions. Magneto-optical Kerr effect measurements show that the maxima of the remanence and coercivity are also along in-plane 〈100〉 film directions. This easy-axis orientation differs from bulk magnetite and films prepared by other techniques, establishing that the magnetic anisotropy can be tuned by film growth.We examine the magnetic easy-axis directions of stoichiometric magnetite films grown on SrTiO3:Nb by infrared pulsed-laser deposition. Spin-polarized low-energy electron microscopy reveals that the individual magnetic domains are magnetized along the in-plane film directions. Magneto-optical Kerr effect measurements show that the maxima of the remanence and coercivity are also along in-plane film directions. This easy-axis orientation differs from bulk magnetite and films prepared by other techniques, establishing that the magnetic anisotropy can be tuned by film growth.

Gold coatings on polymer laser induced periodic surface structures: assessment as substrates for surface-enhanced Raman scattering

We report on the fabrication of gold coated nanostructured polymer thin films and on their characterization as substrates for surface enhanced Raman spectroscopy (SERS). Laser induced periodic surface structures (LIPSS) were obtained on thin polymer films of poly(trimethylene terephthalate) (PTT) upon laser irradiation with the fourth harmonic of a Nd:YAG laser (266 nm, pulse duration 6 ns) resulting in a period close to the incident wavelength. The nanostructured polymer substrates were coated with a nanoparticle assembled gold layer by pulsed laser deposition using the fifth harmonic of a Nd:YAG laser (213 nm, pulse duration 15 ns). Different deposition times resulted in thicknesses from a few nanometres up to several tens of nanometres. Analysis by atomic force microscopy and grazing incident small angle X-ray scattering showed that gold coating preserved the LIPSS relief. The capabilities of the produced nanostructures as substrates for SERS have been investigated using benzenethiol as a test molecule. The SERS signal is substantially larger than that observed for a gold-coated flat substrate. Advantages of this new type of SERS substrates are discussed.

Spectroscopic studies of laser ablation plumes of artwork materials

Studies on the plasma plume created during KrF laser (248 nm) ablation of dosimeter tempera samples in vacuum have been carried out to investigate the basic interactions of the laser with paint materials. Time resolved optical emission spectroscopy (OES) was used to measure the translational velocity of electronically excited transients in the plasma plume. Laser-induced fluorescence (LIF) studies using a probe dye laser, allowed to determine the velocities of non-emitting species. The propagation velocities of C2 in the a 3 pu and d 3 pg electronic states and of excited atomic species are indicative of a high translational temperature. Differences between the velocities of organic and inorganic species and between emissions from the tempera systems and from the pigments as pellets allow to discuss the participation of photochemical mechanisms in the laser irradiation of the paint systems. # 2003 Elsevier Science B.V. All rights reserved.