Effect of molecular weight on the morphological modifications induced by UV laser ablation of doped polymers

This work investigates the effect of polymer molecular weight (M(W)) on the surface morphology of poly(methyl methacrylate) (PMMA) and polystyrene (PS) films doped with iodonaphthalene (NapI) and iodophenanthrene (PhenI) following irradiation in air at 248 nm. In agreement with previous studies, irradiation of PMMA at 248 nm results in surface swelling and bubble formation within the irradiated bulk. Most importantly, the size of bubbles varies sensitively for the different M(W) values, with larger bubbles being formed for the low M(W) systems. Nevertheless, the maximum swelling attains higher values for the high M(W) values (when compared at the corresponding ablation threshold of the systems). Real-time monitoring of transmission of a probing beam shows that morphological changes last longer in the low M(W) polymer. Melting, consistent with a thermal mechanism, occurs, and enough evidence is gathered to provide direct support for the bulk photothermal model, according to which ejection requires that a critical number of bonds is broken. In particular, the observed different morphological effects can be ascribed to the interplay of two factors, namely, of the much more efficient decomposition of the low M(W) polymer to gaseous products and of the dependence of the mechanical polymer properties on M(W). For PS at 308 nm, the changes parallel the ones for PMMA at 248 nm. In contrast, at the strongly absorbed 248 nm, the morphological processes in PS show a less dramatic dependence on M(W). In all, these results are of direct importance for the optimization of laser processing schemes and applications (e.g., tissue processing, laser deposition, laser restoration, etc.).     

A two-color laser photolysis method for determining reaction rates of short-lived intermediates by product analysis: application to the o-quinodimethane problem

A time-delayed, two-color pulse laser photolysis technique was used for a kinetic study of short-lived transient species through product analysis, the determination of the rate constant of the cycloaddition of o-quinodimethane (1) and maleic anhydride (2) in room-temperature solutions. o-Quinodimethane (1) was generated from 1,2-bis[(phenylseleno)methyl]benzene (3) by the irradiation of a pulse of a KrF excimer laser (248 nm) in the presence of excess 2, and a successive pulse of a XeCl excimer laser (308 nm) was irradiated to the reaction mixture after varied delay times from 0 to 0.1 s for the decomposition of the remaining 1 to quench the cycloaddition reaction. The rate constant of the cycloaddition of 1 and 2 was 2.1 x 10(5) M(-1) s(-1), which was obtained by the analysis of the delay-time dependence of the product yields.     

Surface microstructure formation by ps‐ and fs‐laser ablation of an elastomer composite

We investigated the laser ablation of an elastomer composite with picosecond‐ (ps‐) and femtosecond‐ (fs‐) pulsed UV lasers (ps‐laser: λ = 263 nm, τ = 8 ps; fs‐laser: λ = 248 nm, τ = 500 fs). Upon laser irradiation, a unique microstructure on the surface of the elastomer composite (acrylate polymer) containing carbon black (particle size: 18–30 nm) was observed. The laser‐ablated surfaces were analyzed by scanning electron microscopy (SEM) and X‐ray photoelectron spectroscopy (XPS). The formation mechanism is discussed in terms of thermal effects induced by the different pulse durations of the lasers.     

UV laser removal of varnish on tempera paints with nanosecond and femtosecond pulses

Two laser cleaning approaches based on ablation by ultraviolet laser pulses of femtosecond (fs) and nanosecond (ns) durations for the removal of shellac varnish from egg-yolk based tempera paints are investigated. Laser irradiation effects, induced on the varnish layer and on the underlying temperas by multiple pulses in the fs domain at 398 and 265 nm and single pulses in the ns domain at 213 nm, were examined following a spectroanalytical approach. By using optical microscopy, colorimetry and laser induced fluorescence it was found that irradiation of the varnished temperas with fs pulses changes the texture of the varnish surface and results in degradation of the underlying coloured paint. In contrast, operating with pulses of 15 ns at the highly absorbed wavelength of 213 nm, controlled micrometric layer removal of the varnish is possible without noticeable modification of the coloured temperas. These results widen the choice of laser conditions for painting restoration.     

Recent trends and developments in laser ablation-ICP-mass spectrometry

The increased interest in laser technology (e.g. for micro-machining, for medical applications, light shows, CD-players) is a tremendous driving force for the development of new laser types and optical set-ups. This directly influences their use in analytical chemistry. For direct analysis of the elemental composition of solids, mostly solid state lasers, such as Nd:YAG laser systems operating at 1064 nm (fundamental wavelength), 266 nm (frequency quadrupled) and even 213 nm (frequency quintupled) have been investigated in combination with all available inductively coupled plasma mass spectrometers. The trend towards shorter wavelengths (1064 nm - 157 nm) was initiated by access to high quality optical materials which led to the incorporation of UV gas lasers, such as excimer lasers (XeCl 308 nm, KrF 248 nm, ArF 193 nm, and F2 157 nm) into laser ablation set-ups. The flexibility in laser wavelengths, output energy, repetition rate, and spatial resolution allows qualitative and quantitative local and bulk elemental analysis as well as the determination of isotope ratios. However, the ablation process and the ablation behavior of various solid samples are different and no laser wavelength was found suitable for all types of solid samples. This article highlights some of the successfully applied systems in LA-ICP-MS. The current fields of applications are explained on selected examples using 266 nm and 193 nm laser ablation systems.     

Recent trends and developments in laser ablation-ICP-mass spectrometry

The increased interest in laser technology (e.g. for micro-machining, for medical applications, light shows, CD-players) is a tremendous driving force for the development of new laser types and optical set-ups. This directly influences their use in analytical chemistry. For direct analysis of the elemental composition of solids, mostly solid state lasers, such as Nd:YAG laser systems operating at 1064 nm (fundamental wavelength), 266 nm (frequency quadrupled) and even 213 nm (frequency quintupled) have been investigated in combination with all available inductively coupled plasma mass spectrometers. The trend towards shorter wavelengths (1064 nm– 157 nm) was initiated by access to high quality optical materials which led to the incorporation of UV gas lasers, such as excimer lasers (XeCl 308 nm, KrF 248 nm, ArF 193 nm, and F₂ 157 nm) into laser ablation set-ups. The flexibility in laser wavelengths, output energy, repetition rate, and spatial resolution allows qualitative and quantitative local and bulk elemental analysis as well as the determination of isotope ratios. However, the ablation process and the ablation behavior of various solid samples are different and no laser wavelength was found suitable for all types of solid samples. This article highlights some of the successfully applied systems in LA-ICP-MS. The current fields of applications are explained on selected examples using 266 nm and 193 nm laser ablation systems.     

INDUCTION OF LAMBDA PROPHAGE NEAR THE SITE OF FOCUSED UV LASER RADIATION

DNA damage from photon scatter or beam spread during UV excimer laser irradiation was investigated using the induction of bacteriophage lambda in E. coli BR339. Prophage induction in these cells leads to the production of beta-galactosidase which can be detected colorimetrically by the application of appropriate substrates. An agar surface overlayed with BR339 cells was placed at various distances from the focal point of a converging lens and exposed to either 193 or 248 nm laser radiation. Energy densities ranging from approximately 5 mJ/cm2 to 30 J/cm2 were used. Ablation with 193 nm laser radiation produced an 800 microns wide clear 'trench' surrounded by a 500 microns zone of cells in which lambda had been induced. Following ablation with 248 nm laser radiation, the zone of induction was several millimeters wide. Exposures to 193 nm radiation at 170 mJ/cm2/pulse produced visible ablation of the agar surface at 1.7 J/cm2. Lambda induction was observed surrounding cleared ablation areas. The presence of induction in this system suggests that both 248 and 193 nm excimer laser radiation delivered at high energy densities has sufficient spread or scatter to damage DNA in cells surrounding areas of ablation.     

Surface properties of polymers treated with F2 laser

Selected polymers (polyethylene‐PE, polypropylene‐PP, polytetrafluoroethylene‐PTFE, polystyrene‐PS and polyethylenterephthalate‐PET) were irradiated with the linearly polarized light of a pulsed 157 nm F₂ laser. The irradiation results in degradation of polymers and ablation of polymer surfaces. Contact angle, measured by goniometry, was studied as a function of the number of laser pulses. The volume of the ablated polymer layer was determined by gravimetry. Changes in surface morphology and roughness were observed using atomic force microscopy. Surface chemistry of the samples was investigated by electrokinetic analysis and by XPS. While PET and PE exhibit small ablation, the ablation of PS and PTFE is more significant, and the most pronounced ablation is observed on PP. Contact angle of all polymers, with the only exception of PP, is a decreasing function of the number of laser pulses up to 2000 pulses. Laser irradiation leads to a refinement of the polymer surface morphology and a decrease of their surface roughness. Electrokinetic analysis and PS show changes in the surface chemistry of polymers after the laser treatment. Copyright © 2011 John Wiley & Sons, Ltd.     

Morphological Investigation of Poly[methyl(H)silane-co-diphenylsilane] Irradiated by XeCl Excimer Laser

The morphological properties of poly[methyl(H)silane-co-diphenylsilane] copolymer (PSH) under XeCl (308 nm) laser irradiation were investigated. For this purpose, PSH films were exposed to XeCl excimer laser, 308 nm, at various UV doses (122 and 366 mJ/cm²), with 11 and 33 mJ/pulse and 1 Hz pulse repetition rate. The morphology of the PSH film surface was investigated by the atomic force microscopy (AFM) technique. AFM identifies that the films of the copolymer form a wormlike morphology before irradiation and conical defects are created on the polymer surface and grow with the laser irradiation.     

ArF and KrF laser-induced gas-phase photolysis of selenophene and tellurophene: extrusion of Te and Se and intramolecular 1,3-H shift competing with beta-C-C cleavage in C4H4 residue

ArF (193 nm) and KrF (248 nm) laser-induced photolysis of gaseous selenophene and tellurophene (C4H4M, M=Se and Te) has been examined. It is shown that, unlike thiophene and furan, selenophene and tellurophene cleave both M-C bonds and yield the elemental heteroatom (Se, Te), 1-buten-3-yne, and ethyne. The proposed mechanism involves an intermediate .HC=CH-CH=CH. diradical that decomposes via two competitive pathways, namely, 1,3-H shift to 1-buten-3-yne and beta-cleavage to two molecules of ethyne. It is shown that the relative importance of the channels depends both on the energy of the photon and on the heteroatom. Specifically, the 1,3-H shift/beta-cleavage ratios are 2.3 (193 nm, M=Se), 3.6 (248 nm, M=Se), 1.4 (193 nm, M=Te), and 10.5 (248 nm, M=Te). The inertness of the Te residuum and the high preference for the 1,3-H shift in KrF laser photolysis of tellurophene suggest that this photolysis can serve as a source of the C4H4 diradical for mechanistic studies.     

Inductively coupled plasma mass spectrometric study of non-linear calibration behavior during laser ablation of binary Cu–Zn Alloys

Laser ablation behavior of a suite of 10 Cu–Zn binary alloys was studied using inductively coupled plasma mass spectrometry. Three laser systems (20 ns KrF excimer, 6 ns and 35 ps Nd:YAG) were used for ablation. Non-linear calibration plots for both Cu and Zn were observed using all three lasers, despite significant differences in laser ablation mechanisms and good stoichiometry of ablated mass. Crater volume measurements were used to determine the amount of mass removed during repetitive laser ablation from each sample. A change in mass ablation rate for samples with different composition explains observed phenomena. Despite the differences in ablation behavior of these alloys, linear calibration curves were obtained when Zn signal intensity was normalized to signal intensity of Cu or to crater volume.     

Deep UV photoresists based on poly(dl-tert-butyl fumarate)

Poly(di-tert-butyl fumarate) was prepared and evaluated as a potential candidate as a deep UV photoresist. Although this polymer displayed excellent sensitivity, the polymer was found to exhibit poor dry etch resistance. Copolymers of di-tert-butyl fumarate with either allyltrimethylsilane or styrene, and an onium salt as a photoacid generator were synthesized and subsequently evaluated using a 248-nm KrF excimer laser step-and-repeat system (stepper). At 248 nm, the absorbance of ～ 1 μm thick resist films was only 0.156-0.211. The sensitivities of these resists were 1-4 mJ/cm². The dry etch resistance of these photoresists was comparable to that of conventional positive photoresists based on novolac resins. © 1995 John Wiley & Sons, Inc.     

Material removal and chemical and structural changes induced by irradiation of polymer surfaces with KrF-excimer laser radiation

Holes in polypropylene (PP) and polymethylmethacrylate (PMMA) plates, 0.5 mm in thickness were drilled by irradiation with up to 3000 pulses of KrF-excimer laser radiation (λ = 248 nm) at fluences per pulse ? in the range 0.1–10 J/cm², conditions which yield a laser-induced plasma/vapor plume. The process was analyzed experimentally in terms of material removal rate, optical emission of the laser-induced plasma, hole geometry, debris production at the hole edge, and chemical changes in the polymer induced by the laser irradiation. Additionally, the process was simulated using a model based on degradation of the polymer induced by optical absorption and heating, leading to gas-phase products. Such characteristics as the material removal rate as a function of fluence, the nature of the gas phase products and the deposition of debris were calculated.     

Surface characterisation of laser irradiated SiC ceramics by AES and XPS

Samples of sintered silicon carbide (SSiC) were irradiated with a KrF excimer laser (λ = 248 nm) at energy densities of 10, 15 and 25 J/cm² in He atmosphere. The composition of the near surface region was investigated by Auger electron spectroscopy (AES) and photoelectron spectroscopy (XPS) after lapping, laser irradiation and tribological treatment, respectively. By laser irradiation a surface layer is formed which contains about 30% oxygen. The existence of different bonding states of Si, C and O was established by factor analysis of the AES depth profiles and by XPS. By laser irradiation SiC is decomposed and a siliconoxycarbide with the average composition SiC_3.5O_1.5 is formed. Beneath the oxidised surface layer the nominal elemental composition SiC is found but the sample represents a mixture of Si, graphite and siliconoxycarbide with a small amount of SiC only. Obviously, the decomposition zone exceeds in a depth > 300 nm.     

Photo-detrapping of solvated electrons in an ionic liquid

We studied the dynamics of photo-detrapped solvated electrons in the ionic liquid trimethyl-N-propylammonium bis(trifluoromethanesulfonyl)imide (TMPA-TFSI) using laser flash photolysis. The solvated electrons were produced by the electron photodetachment from iodide via a 248 nm KrF excimer laser. The solvated electron decayed by first-order kinetics with a lifetime of about 240 ns. The spectrum of the solvated electron in the ionic liquid TMPA-TFSI is very broad with a peak around 1100 nm. After the 248 nm pulse, a 532 nm pulse was used to subsequently detrap the solvated electrons. After the detrapping pulse, quasi-permanent bleaching was observed. The relative magnitude of the bleaching in the solvated electron absorbance was measured from 500 to 1000 nm. The amount of bleaching depends on the probe wavelength. The fraction of bleached absorbance was larger at 500 nm than that at 1000 nm, suggesting that there are at least two species that absorb 532 nm light. We discuss the present results from viewpoint of the heterogeneity of ionic liquids.     

Formation of conjugated polyene and polyyne structure by KrF excimer laser-induced dehydrochlorination on polyvinylidenechloride film

The surface dehydrochlorination of poly(vinyldenchloride) film was performed to produce a conjugated polyyne and polyene structures by photo-irradiation with a KrF excimer laser at 248 nm in a vacuum chamber. The reaction was confirmed by detection of HCl with a mass spectrometer and by measurement of chlorine content on the film with X-ray photoelectron spectroscopy. UV-visible absorption spectroscopy for the laser-treated film showed the formation of new broad absorption bands in the visible and near IR region, indicating that sequential dehydrochlorination induced the formation of conjugated carbon multiple bonds in the polymer chain. Its conjugation number is estimated to be 30 for a triple bond and 10–25 for a double bond from the peak positions on the Raman spectrum of the film. ESR spectra of laser-irradiated PVDC powder also showed long-lived radicals having a narrow band width (ΔH_pp = 0.15 mT), suggesting that the radicals were delocalized on the conjugated bonds. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2483–2487, 1998     

Laser photodissociation of PuF6 and transient product absorption in the visible

PuF₆ moleculs were flash-photolyzed in a static cell at 248 nm using a KrF excimer laser. The absorption by the transient product was detected in the wavelength region of 500–850 nm by probing the photolysis volume coaxially with a cw source. A measurement of the product absorption cross section at 632.8 nm is shown. The product absorption decay is discussed in terms of primary photolytic reactions among the product species.     

Structure induced by irradiation of femtosecond laser pulse in dyed polymeric materials

We investigated the structures induced by an irradiation of a near‐infrared (NIR) femtosecond laser pulse in dye‐doped polymeric materials {poly(methyl methacrylate) (PMMA), thermoplastic epoxy resin (Epoxy), and a block copolymer of methyl methacrylate and ethyl acrylate‐butyl acrylate [p(MMA/EA‐BA) block copolymer]}. Dyes used were classified into two types—type 1 with absorption at 400 nm and type 2 with no absorption at 400 nm. The 400‐nm wavelength corresponds to the two‐photon absorption region by the irradiated NIR laser pulse at 800 nm. Type 1 dye‐doped PMMA and p(MMA/EA‐BA) block copolymer showed a peculiar dye additive effect for the structures induced by the line irradiation of a NIR femtosecond laser pulse. On the contrary, dye‐doped Epoxy did not exhibit a dye additive effect. The different results among PMMA, p(MMA/EA‐BA) block copolymer, and Epoxy matrix polymers are supposed to be related to the difference of electron‐acceptor properties. The mechanism of this type 1 dye‐additive‐effect phenomenon for PMMA and p(MMA/EA‐BA) block copolymer is discussed on the basis of two‐photon absorption of type 1 dye at 400 nm by the irradiation of a femtosecond laser pulse with 800 nm wavelength and the dissipation of the absorbed energy to the polymer matrix among various transition processes. Dyes with a low‐fluorescence quantum yield favored the formation of thicker grating structures. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2800–2806, 2002     

Determination of the photochemical efficiency of o-quinodimethane ring closure in room-temperature solutions by using time-delayed, two-color photolysis technique

Photochemical efficiency of o-quinodimethane (3) ring closure at room temperature was determined by using a time-delayed, two-color photolysis technique. o-Quinodimethane (3) was generated by the photolysis of 1,2-bis[(phenylseleno)methyl]benzene (1) by a KrF (248 nm) laser pulse and thus-generated 3 was photolyzed by a subsequent XeCl (308 nm)/XeF (351 nm) laser pulse with varying delay time of 0 to 3 s. The time profile of 3 was monitored by the chemical analyses of benzocyclobutene (5) (a photochemical product of 3), which was formed by a one-photon process, and the spiro dimer of 3 (4) (a thermal product of 3) in the two-color photolysis experiments. The time profile of 3 followed a second-order decay kinetics. The photochemical efficiency was obtained by the analysis of the delay-time dependence of the product yields; those of the consumption of 3 and the conversion 3-->5 by a single pulse of the excimer laser were 81% and 5.7% for the XeCl laser, and 73% and 2.3% for the XeF laser. This difference was attributed to the different excited states involved in the photolysis. In contrast to the photolysis of 3 in argon or rigid organic matrixes, it was revealed that photochemical conversion 3-->5 was not the main path in the solutions, and intermolecular reactions predominated.     

Fast Imaging of Laser-induced Plasma Emission from a ZnO Target

The spatio-temporal evolution of plasma plume laser ablation zinc oxide target was investigated by ICCD camera fast imaging. The plasma was created by a KrF excimer laser of 248 nm wavelength and 25 ns pulse. The laser fluence was set at 2 J/cm². This study was performed under vacuum and oxygen atmosphere at a pressure range of 10^− 6 to 10 mbar.Free expansion, splitting and stopping of the plume were observed at different pressures and time delays following the laser pulse. Moreover, depending on the gas pressures, the photography shows some turbulence for given time delays in the front edge of the plasma while at 5 and 10 mbar the whole plasma edge is perturbed. Rayleigh–Taylor instability is proposed as an explanation to this observed effect. A time integrated emission spectroscopy diagnostic has been also used to identify plasma species. A plasma emission spectrum shows the presence of Zn⁺, Zn and O emission lines both in vacuum and in O₂ atmosphere. As the distance from the target surface increases the Zn⁺ emission line disappears.