Controlling the reversible wetting capability of smart photochromic-polymer surfaces by micro patterning

We demonstrate the wetting behavior control of polymer surfaces doped with photochromic molecules by modifying the surface patterning features introduced by soft molding lithography. Such surfaces enhance their hydrophilicity upon UV irradiation due to conversion of the non-polar spiropyran dopant molecules to their polar merocyanine isomers. The process is reversed upon visible light irradiation. By changing the topological parameters of the introduced pattern, one achieves surface tuning from hydrophobic to hydrophilic situations. The difference for the contact angles between UV- and green-irradiated surfaces may become significantly higher than for the flat surfaces, for the specific patterning parameters analyzed. PACS 42.62.-b; 68.08.Bc; 83.50.Uv; 42.70.Jk; 42.70.Gi     

Photocontrolled mechanical phenomena in photochromic doped polymeric systems

This work examines volume changes at the sub-micron scale, induced photochemically in polymeric matrices doped with photochromic molecules. To achieve this, spiropyran is employed as a photochromic molecule embedded in polyethylmethacrylate-co-methylacrylate (PEMMA) matrices. Spiropyran can be reversibly interconverted to merocyanine, its coloured isomer, by irradiation at 248 nm and 532 nm, correspondingly. It is demonstrated that the interconversion between the two forms activates volume changes in the polymer matrix. To this end, off-axis reflection holographic interferometry is employed as a sensitive probe of the induced volume changes. This scheme provides a novel method for controlling sub-micron volume changes reversibly, as required in several microactuator designs. Received: 17 April 2002 / Accepted: 18 April 2002 / Published online: 10 September 2002 RID="*" ID="*"Corresponding author. Fax: +30-810/391-318, E-mail: nassia@iesl.forth.gr     

Three-dimensional reversible laser micromachining with subnanojoule femtosecond pulses based on two-photon photochromism

Three-dimensional reversible laser micromachining of polymer materials based on two-photon photochromism is demonstrated. Unamplified 60-fs, 0.5-nJ pulses of 790-nm Ti:sapphire laser radiation are used to induce a refractive-index change in a polymethyl methacrylate (PMMA) sample doped with spiropyran molecules through a two-photon absorption process. Waveguides are written in the bulk of spiropyran-doped PMMA samples by scanning these samples with respect to a tightly focused Ti:sapphire laser beam. Laser-induced fluorescence is used for on-line monitoring of the laser-micromachining process. The structures written in photochromic samples can be erased and reconfigured due to the reversibility of the photochromic effect. Received: 23 April 2003 / Published online: 6 June 2003 RID="*" ID="*"Corresponding author. Fax: +7-095/939-51-74, E-mail: zheltikov@top.phys.msu.su     

Processing of W/Si and Si/W bilayers and multilayers with single and multiple excimer-laser pulses

Interdiffusion phenomena, thermal damage and ablation of W/Si and Si/W bilayers and multilayers under XeCl-excimer laser (=308 nm) irradiation at fluences of 0.15, 0.3 and 0.6 J/cm² were studied. Samples were prepared by UHV e-beam evaporation onto oxidized Si. The thickness of W and Si layers and the total thickness of the structures were 1–20 nm and 40–100 nm, respectively. 1 to 300 laser pulses were directed to the same irradiation site. At 0.6 J/cm² the samples were damaged even by a single laser pulse. At 0.3 J/cm² WSi₂ silicide formation, surface roughening and ablation were observed. The threshold for significant changes depends on the number of pulses: it was between 3–10 pulses and 10–30 pulses for bilayers with W and Si surfaces, respectively, and more than 100 pulses for multilayers with the same total thickness of tungsten. At 0.15 J/cm² the periodicity of the multilayers was preserved. Temperature profiles in layered structures were obtained by numerical simulations. The observed differences of the resistance of various bilayers and multilayers against UV irradiation are discussed.     

Nano- and femtosecond UV laser pulses to immobilize biomolecules onto surfaces with preferential orientation

By relying on the photonic immobilization technique of antibodies onto surfaces, we realized portable biosensors for light molecules based on the use of quartz crystal microbalances, given the linear dependence of the method on the laser pulse intensity. Here, we compare the quality of the anchoring method when using nanosecond (260 nm, 25 mJ/pulse, 5 ns, 10 Hz rep. rate) and femtosecond (258 nm, 25 μJ/pulse, 150 fs, 10 kHz rep. rate) laser source, delivering the same energy to the sample with the same average power. As a reference, we also tethered untreated antibodies by means of the passive adsorption. The results are striking: When the antibodies are irradiated with the femtosecond pulses, the deposition on the gold plate is much more ordered than in the other two cases. The effects of UV pulses irradiation onto the antibodies are also analyzed by measuring absorption and fluorescence and suggest the occurrence of remarkable degradation when nanosecond pulses are used likely induced by a larger thermal coupling. In view of the high average power required to activate the antibodies for the achievement of the photonic immobilization technique, we conclude that femtosecond rather than nanosecond laser pulses have to be used.     

Patterning and modification of PDMS surface through laser micromachining of silicon masters and molding

We describe preparation of micro patterned PDMS sample surfaces and their chemical modification for the purposes of increased hydrophobicity. The process includes ablation of micrometer sized patterns on a silicon master by pulsed radiation from a Nd:YAG laser, transfer of the patterns to PDMS through molding, and chemical modification of the topmost surface layers of the polymer sample by further laser irradiation and UV/ozone treatment. The samples were characterized by XPS, FTIR, contact angle measurements, optical microscopy and SEM. The study shows the feasibility of the method to manufacture regular patterns with micron-sized cylindrical pillars and to control surface composition. In the absence of chemical modification of the surfaces due to preparation, we compare the effect of increased roughness on the contact angle with theoretically predicted values. Samples with patterned and chemically modified surfaces due to UV/ozone treatment show reduced hydrophobicity. PACS 52.38.Mf; 81.65.Cf; 81.05.Lg     

Effect of XeCl laser irradiation on the defect structure of Nd:YAG crystals

This paper presents the effect of XeCl laser irradiation on Nd:YAG single crystal samples with various number of pulses at different repetition rates and laser fluences. Effects of the irradiation on the optical and structural properties of the crystal are analyzed by UV–vis-NIR spectroscopy. Annihilation of some point defects of the crystal structure is observed following laser irradiation at a fluence of 100 mJ cm⁻² with 100 and 500 pulses. Increasing the laser fluence and pulse numbers leads to saturation and new defects are found to be formed in the crystal. Additional absorption spectra of the irradiated samples show that oxygen vacancies in the Nd:YAG crystals are removed during the low-dose irradiation. The laser irradiation is compared to the thermal annealing process for Nd:YAG crystal modification. Additional absorption spectrum of an annealed sample reveals that induced negative absorption band at 236 nm is correlated with the annihilation of the oxygen vacancy center. Our results also demonstrate that XeCl laser treatment has several advantages upon annealing at high temperatures in the Nd:YAG crystal quality improvement. Thus, the present work can give a new approach to modify Nd:YAG crystals to be used in a wide variety of solid-state laser engineering.     

飞秒激光在6H SiC晶体表面制备纳米微结构

激光诱导周期性纳米微结构在多种材料包括电介质、半导体、金属和聚合物中观察到。研究了800nm和400nm飞秒激光垂直聚焦于6H SiC晶体表面制备纳米微结构。实验观察到800nm和400nm线偏光照射样品表面分别得到周期为150nm和80nm的干涉条纹,800nm圆偏振激光单独照射样品表面得到粒径约100nm的纳米颗粒。偏振相互垂直的800nm和400nm激光同时照射晶体得到粒径约100nm的纳米颗粒阵列,该纳米阵列的方向随400nm激光强度增加而向400nm偏振方向偏转。利用二次谐波的观点对以上纳米结构的形成给出了解释。     

A femtosecond stimulated raman spectrograph for the near ultraviolet

The design of a femtosecond stimulated Raman spectrograph (FSRS) optimized for measurements in the near UV is presented. It features a 387.5 nm Raman pump pulse causing a (pre-)resonance enhancement for molecular absorbing in the UV. As many photoreactive molecules absorb there, the set-up is particularly suited to study photochemical reactions. The 387.5 nm pulses are generated by frequency adding two femtosecond laser pulses with linear chirps, equal in magnitude but opposite in sign. This results in intense and spectrally narrow (∼10 cm^-1) Raman pump pulses which allow recording of Raman spectra with a good spectral resolution. The power of the spectrograph to trace ultrafast photoreactions is illustrated by measurements on the photochemistry of o-nitrobenzaldehyde. PACS 33.20.Fb; 39.30.+w     

Ultrafast changes in the optical properties of a titanium surface and femtosecond laser writing of one-dimensional quasi-periodic nanogratings of its relief

One-dimensional quasi-periodic nanogratings with spacings in the range from 160 to 600 nm are written on a dry or wet titanium surface exposed to linearly polarized femtosecond IR and UV laser pulses with different surface energy densities. The topological properties of the obtained surface nanostructures are studied by scanning electron microscopy. Despite the observation of many harmonics of the one-dimensional surface relief in its Fourier spectra, a weak decreasing dependence of the first-harmonic wavenumber (nanograting spacing) on the laser fluence is found. Studies of the instantaneous optical characteristics of the material during laser irradiation by measuring the reflection of laser pump pulses and their simulation based on the Drude model taking into account the dominant interband absorption allowed us to estimate the length of the excited surface electromagnetic (plasmon-polariton) wave for different excitation conditions. This wavelength is quantitatively consistent with the corresponding nanograting spacings of the first harmonic of the relief of the dry and wet titanium surfaces. It is shown that the dependence of the first-harmonic nanograting spacing on the laser fluence is determined by a change in the instantaneous optical characteristics of the material and the saturation of the interband absorption along with the increasing role of intraband transitions. Three new methods are proposed for writing separate subwave surface nanogratings or their sets by femtosecond laser pulses using the near-threshold nanostructuring, the forced adjustment of the optical characteristics of the material or selecting the spectral range of laser radiation, and also by selecting an adjacent dielectric.     

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

The formation of laser-induced periodic surface structures (LIPSS) upon irradiation of silicon wafer surfaces by linearly polarized Ti:sapphire femtosecond laser pulses (pulse duration 130 fs, central wavelength 800 nm) is studied experimentally and theoretically. In the experiments, so-called low-spatial frequency LIPSS (LSFL) were found with periods smaller than the laser wavelength and an orientation perpendicular to the polarization. The experimental results are analyzed by means of a new theoretical approach, which combines the widely accepted LIPSS theory of Sipe et al. with a Drude model, in order to account for transient (intra-pulse) changes of the optical properties of the irradiated materials. It is found that the LSFL formation is caused by the excitation of surface plasmon polaritons, SPPs, once the initially semiconducting material turns to a metallic state upon formation of a dense free-electron-plasma in the material and the subsequent interference between its electrical field with that of the incident laser beam resulting in a spatially modulated energy deposition at the surface. Moreover, the influence of the laser-excited carrier density and the role of the feedback upon the multi-pulse irradiation and its relation to the excitation of SPP in a grating-like surface structure is discussed.     

Two-photon Induced UV Fluorescence in Photo-active Spiropyran Molecules

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The potential of UV femtosecond laser ablation for varnish removal in the restoration of painted works of art

Despite significant advances, laser ablation with nanosecond pulses presents limitations in dealing with the restoration of classes of painted works of art, such as paintings with a very thin layer of varnish. Femtosecond laser processing promises the means for overcoming such limitations. To this end, femtosecond ablation of two typical varnishes, dammar and mastic, is examined. For these varnishes, processing by Ti:Sapphire irradiation (800 nm) turns out to be ineffective. In contrast, irradiation with 248 nm ∼500 fs laser pulses results in a higher etching resolution (etching rates of ∼1 μm/pulse or less). For irradiation with few laser pulses at moderate laser fluences, etched morphology is far smoother than in the processing with nanosecond laser pulses. Furthermore, chemical modifications are considerably reduced (by nearly an order of magnitude), and exhibit a number of additional novel differences. Both etching rates and extent of chemical modifications are largely independent of varnish absorptivity. In all, femtosecond UV laser irradiation is indicated to hold a high potential, offering new perspectives for the restoration of painted works of art. Finally, a tentative model is advanced accounting in a consistent way for the observations.     

Femtosecond laser processing of nitride-based thin films to improve their tribological performance

The ability of femtosecond laser pulses to pattern coated tribological surfaces in order to improve their wear behavior was investigated. Experiments were performed with a Ti:sapphire laser (wavelength: 800 nm, energy density: 2 J/cm², pulse duration: 100 fs) on TiN- and on TiCN-coated surfaces. Morphological analyses of the laser-treated surfaces were carried out and did not reveal any film delamination or other coating damage after laser processing. Tribological tests simulating rapidly increasing contact pressures under boundary friction were performed on both unpatterned and laser-patterned coated surfaces using a steel counter body. The patterned surfaces showed significantly better tribological performance with respect to stability and the value of the friction coefficient during testing. EDX analyses of the tested unpatterned samples revealed complete coating removal and material transfer from the counter body to the sample surface. In the case of the laser-patterned surfaces, only slight coating damage and an accumulation of debris from the steel counter body in the laser-induced pores were observed. PACS 42.62.Cf; 81.40.Wx     

Raman characterization of localized CdS nanostructures synthesized by UV irradiation in sol–gel silica matrices

A new technique of UV irradiation has been used for the first time to create microstructures of CdS nanoparticles in bulk xerogels. Porous silica matrices, which were first soaked in a solution containing CdS precursors, were subjected to irradiation using a nanopulsed ArF laser with a wavelength of 193 nm and a repetition rate of 10 Hz. Resonant micro‐Raman spectra, recorded using the 325‐nm line of a He‐Cd laser (with a continuous power less than 0.5 mW so as to avoid the thermal formation of nanoparticles) made it possible to identify CdS nanoparticles within the inscribed yellow zones and also to estimate the average particle size (3.6 to 8.0 nm, depending on the number of UV pulses used). The emission of CdS particles embedded in the silica matrix under excitation at 351.1 nm was studied by photoluminescence spectroscopy. It was then possible to show the effect of the number of pulses on the electronic structure of the nanocrystals. Finally, Raman spectra were used to monitor the structural changes in the silica matrix caused by the irradiation. It was found that the pulsed UVirradiation resulted in a local densification of the matrix, which was compensated for by a depolymerization process of the Si O Si network. In spite of this pulsed irradiation and the resulting structural depolymerization, no apparent ablation or cracking of the samples was observed. Copyright © 2010 John Wiley & Sons, Ltd.     

Observations of surface modifications induced by the multiple pulse irradiation using a soft picosecond x-ray laser beam

To study the interactions between picosecond soft x-ray laser (SXRL) beams and material surfaces, gold (Au), copper (Cu), and silicon (Si) surfaces were irradiated with SXRL pulses having a wavelength of 13.9 nm and a duration of ～7 ps. Following irradiation, the surfaces of the substrates were observed using a scanning electron microscope and an atomic force microscope. With single pulse irradiation, ripple-like structures were formed on the Au and Cu surfaces. These structures were different from previously investigated conical structures formed on an Al surface. In addition, it was confirmed that the development of modified structures, i.e., growth of hillocks on the Au and Cu surfaces, was observed after multiple SXRL pulse exposures. However, on the Si surface, deep holes that seemed to be melted structures induced by the accumulation of multiple pulses of irradiations were found. Therefore, it was concluded that SXRL beam irradiation of various material surfaces causes different types of surface modifications, and the changes in the surface behaviors are attributed to the differences in the elemental properties, such as the attenuation length of x-ray photons.     

Nanofoaming dynamics in biopolymers by femtosecond laser irradiation

We have recently shown that irradiation of self-standing films of the biopolymers collagen and gelatine with single femtosecond laser pulses produces a nanofoaming layer with regular bubble size which can be controlled by wavelength selection. Following these initial studies, here we report on the temporal evolution of the foaming effect by measurements in situ and in real time of the change in the transmittance of a cw probe HeNe laser through the irradiated films. Self standing films of the biopolymers were irradiated with 90 fs laser pulses at 800, 400, and 266 nm. For fluences below and above the modification threshold a permanent attenuation of the transmission occurs (increasing with fluence). The initial decay of the transmission is fast (around few tens of ns), and is followed by dynamics in the longer timescale (micro and milliseconds). The temporal evolution of the transmission measured upon fs laser irradiation is similar with that determined in the irradiation of the biopolymer films at 248 nm with 25 ns laser pulses. The method allows separating in time the different processes occurring after irradiation that lead to a permanent nanofoaming structure, while the results allow us to understand the mechanisms of femtosecond laser processing of the biopolymers and their interest in biomedical applications.     

Submicron foaming in gelatine by nanosecond and femtosecond pulsed laser irradiation

We compare the foaming characteristics induced by irradiation with single ns and fs laser pulses of UV, VIS and IR wavelengths on gelatines differing in gel strength (bloom values 75 and 225) and in crosslinking degree. We have observed that while laser irradiation with nanoseconds leads to the formation of a microfoam layer at 266 nm, and melting and crater formation at longer wavelengths (532 and 1064 nm), fs pulse irradiation leads to submicron foaming at all wavelengths studied (266, 400 and 800 nm). These results show the possibility of controlling the submicrometric foam structure in this biomaterial and can shed light into the working mechanisms of fs laser nanoprocessing in biomaterials, where increase of temperature, thermoelastic stress generation, and stress-induced bubble formation are mediated by the generated plasma.     

Effect of fluence on the discoloration of marble cleaned with UV lasers

The effect of fluence level on the discoloration of marble surfaces after the removal of the encrustation by 355 nm laser pulses is comparatively studied. Considering the thermochemical reaction possibly occurring in the encrustation during laser irradiation, the mechanism responsible for the discoloration of the cleaned marble surface is analyzed. The reduction of iron oxides by graphite plays a key role in determining the final color of the cleaned marble surface. A two-dimensional laser ablative cleaning model including the reaction heat is applied to calculate the temperature distribution during laser heating. The kinetics of the thermochemical reaction is estimated based on the simulated temperature field. The occurrence of the thermochemical reaction is also verified indirectly with experiments. The marble surfaces before and after laser irradiation are characterized in terms of the chemical components through surface enhanced Raman spectroscopy. The surface color is measured with a chromameter using a 1976 CIE L^*a^*b^* color system. The proposed mechanism is also applied to numerically analyze the severe discoloration of marble cleaned with laser pulses at 1064 nm.     

One-way optoelectronic switching of photochromic molecules on gold

We investigate photochromic molecular switches that are self-assembled on gold. We use two experimental techniques; namely, the mechanically controllable break-junction technique to measure electronic transport, and UV/Vis spectroscopy to measure absorption. We observe switching of the molecules from the conducting to the insulating state when illuminated with visible light (lambda=546 nm), in spite of the gold surface plasmon absorption present around this wavelength. However, we fail to observe the reverse process which should occur upon illumination with UV light (lambda=313 nm). We attribute this to quenching of the excited state of the molecule in the open form by the presence of gold.