Nanosecond and femtosecond UV laser ablation of polymers: Influence of molecular weight

We examine the nanosecond and femtosecond UV laser ablation of poly(methyl methacrylate) (PMMA) as a function of molecular weight (M_w). For laser ablation with nanosecond laser pulses, at the excimer wavelengths 248 nm and 193 nm, we show that high temperatures develop; yet the dynamics of material ejection differs depending on polymer M_w. The results on the nanosecond ablation of polymers are accounted within the framework of bulk photothermal model and the results of molecular dynamics simulations. Turning next to the 248 nm ablation with 500 fs laser pulses, the ablation threshold and etching rates are also found to be dependent on polymer M_w. In addition, ablation results in morphological changes of the remaining substrate. Plausible mechanisms are advanced.     

Morphological and chemical modifications and plume ejection following UV laser ablation of doped polymers: Dependence on polymer molecular weight

This work investigates the effect of polymer molecular weight (M_W) on the morphological and chemical modifications and on the plume ejection of doped polymethyl methacrylate (PMMA), and polystyrene (PS) films following irradiation at 248 nm. Micro-bubbles develop in the irradiated films of the low absorbing PMMA-based substrates. The extent and kinetics of the observed morphological changes are respectively larger and last longer in the low M_W polymer, as evidenced by optical microscopy and real-time monitoring of transmission of a CW laser. The changes observed in the Raman spectra upon irradiation indicate that degradation occurs to a higher extent in larger M_W polymers. Laser induced fluorescence (LIF) probing of the plume reveals the presence of NapH and PhenH products from, respectively, NapI- and PhenI-doped films and a slower ejection process in the plume of low M_W polymer. For highly absorbing PS, a less dramatic dependence on M_W is observed. Results are discussed in the framework of the bulk photothermal model, according to which ejection requires a critical number of bonds to be broken.     

Examination of photoproducts in the ablation plume of doped PMMA

Optical emission and laser-induced fluorescence spectroscopies (OES and LIF) are employed to examine the plume ejected into vacuum upon UV pulsed laser ablation (248 nm, 20 ns, and 266 nm, 5 ns) of poly(methyl methacrylate) PMMA films doped with photostable compounds naphthalene (NapH) and phenanthrene (PhenH), and their photolabile iodide derivatives iodonaphthalene (NapI) and iodophenanthrene (PhenI). Spontaneous emissions observed in the irradiation of NapI and PhenI sensitised films can be assigned to excited products resulting from photodissociation of the dopants and to excited C₂, CH, and CN radicals. The presence in the plume of ground state products is revealed by LIF upon excitation at 266 nm. Measurements of the dependence of the spontaneous and LIF emissions on distance to the surface, ablation fluence, and flight velocities of species are discussed with reference to the mechanistic implications derived from the measurements. PACS 52.38.Mf; 61.82.Pv; 82.50     

Examination of the influence of molecular weight on polymer laser ablation: polystyrene at 248 nm

Following previous studies on the influence of the polymer molecular weight (M_W) on the ablation of poly(methyl methacrylate) (PMMA) at 248 nm, this work extends the examination to the ablation of polystyrene (PS) at 248 nm. The ablation threshold and the etching rates are found to be nearly independent of M_W. Optical microscopy demonstrates an excellent crater morphology, few small bubbles are formed on the surface of the low M_W. Examination of the formation kinetics of products in the irradiation of samples doped with the photoreactive iodophenanthrene demonstrates that high temperatures develop upon irradiation, suggesting that thermal mechanism dominates in the ablation of PS at 248 nm. In similarity to the etching rates, the attained temperatures are largely independent of the PS M_W. The factors for the weak dependence of the process on PS M_W are discussed.     

Effective biaxial modulus and strain energy density of ideally (h k l)-fiber-textured cubic polycrystalline films

The effective biaxial modulus (M_eff) and strain energy density (W) of cubic polycrystalline films with ideally (h k l) fiber textures are estimated using Vook-Witt (VW) grain interaction model and the data are compared with those derived from Voigt, Reuss and Voigt-Reuss-Hill (VRH) models. Numerical results show that the VW average of M_eff for ideally (1 0 0)- or (1 1 1)-fiber-textured films is identical to the VRH average of M_eff. For (1 1 0) and (1 1 2) planes, however, the VW average of M_eff for (1 1 0)-fiber-textured film is larger than that of (1 1 2)-fiber-textured film when the Zener anisotropic factor (A_R) is not equal to 1. Furthermore, M_eff and W exhibit incremental tendencies with the increase of the orientation factor (Γ_h k l) for the [h k l] axis when A_R > 1, implying that M_eff and W have the minimums on the (1 0 0) plane. Reversely, M_eff and W decrease with the increasing Γ_h k l when A_R < 1. This means that M_eff and W on (1 1 1) plane have the minimums.     

Local chemical transformations in poly(dimethylsiloxane) by irradiation with 248 and 266 nm

Poly(dimethylsiloxane) (PDMS) has been irradiated with a frequency quadrupled Nd:YAG laser and a KrF^*-excimer laser at a repetition rate of 1 Hz. The analysis of ablation depth versus pulse number data reveals a pronounced incubation behavior. The thresholds of ablation (266 nm: 210 mJ cm⁻², 248 nm: 940 mJ cm⁻²) and the corresponding effective absorption coefficients α_eff (266 nm: 48900 cm⁻¹, 248 nm: 32700 cm⁻¹, α_lin = 2 cm⁻¹) were determined. The significant differences in the ablation thresholds for both irradiation wavelengths are probably due to the different pulse lengths of both lasers. Since the shorter pulse length yields a lower ablation threshold, the observed incubation can be due to a thermally induced and/or a multi-photon absorption processes of the material or impurities in the polymer.Incubation of polymers is normally related to changes of the chemical structure of the polymer. In the case of PDMS, incubation is associated with local chemical transformations up to several hundred micrometers below the polymer surface. It is possible to study these local chemical transformations by confocal Raman microscopy, because PDMS is transparent in the visible. The domains of transformation consist of carbon and silicon, as indicated by the appearance of the carbon D- and G-bands between 1310 and 1610 cm⁻¹, a band appearing between 502 and 520 cm⁻¹ can be assigned to mono- and/or polycrystalline silicon.The ablation products, which are detected in the surroundings of the ablation crater consist of carbon and amorphous SiO_x (x ≈ 1.5) as detected by infrared spectroscopy.     

The influence of UV-irradiation and support type on surface properties of poly(methyl methacrylate) thin films

Thin poly(methyl methacrylate) (PMMA) films were prepared by a solution casting on different supports (glass and aluminium plates with different gloss). UV-irradiation (λ = 254 nm) was used for polymer modification. Surface properties of PMMA were studied by contact angle measurements, attenuated total reflection infrared spectroscopy and optical microscopy. It was found that support type has no influence on surface properties of virgin PMMA, however, the changes in these properties were observed during UV modification of polymer film. The most efficient photochemical reactions appeared in sample placed on the rough Al, whereas the smallest effect was observed in polymer on the glass.     

Nanoimprint lithography using IR laser irradiation

A new technique called “infrared laser-assisted nanoimprint lithography” was utilised to soften the thermoplastic polymer material mR-I 8020 during nanoimprint lithography. A laser setup and a sample holder with pressure and temperature control were designed for the imprint experiments. The polymer was spin coated onto crystalline Si <1 1 1> substrates. A prepatterned Si <1 1 1> substrate, which is transparent for the CO₂ laser irradiation, was used as an imprint stamp as well. It was shown, that the thermoplastic resist mR-I 8020 could be successfully imprinted using the infrared CW CO₂ laser irradiation (λ = 10.6 μm). The etching rate of the CO₂ laser beam irradiated mR-I 8020 resist film under O₂ RF (13.56 MHz) plasma treatment and during O₂ reactive ion beam etching was investigated as well.     

Femtosecond laser patterning of Ta0.1W0.9Ox/ITO thin film stack

Selective laser patterning of thin films in a multilayered structure is an emerging technology for process development and fabrication of optoelectronics and microelectronics devices. In this work, femtosecond laser patterning of electrochromic Ta_0.1W_0.9O_x film coated on ITO glass has been studied to understand the selective removal mechanism and to determine the optimal parameters for patterning process. A 775 nm Ti:sapphire laser with a pulse duration of 150 fs operating at 1 kHz was used to irradiate the thin film stacks with variations in process parameters such as laser fluence, feedrate and numerical aperture of objective lens. The surface morphologies of the laser irradiated regions have been examined using a scanning electron microscopy and an optical surface profiler. Morphological analysis indicates that the mechanism responsible for the removal of Ta_0.1W_0.9O_x thin films from the ITO glass is a combination of blistering and explosive fracture induced by abrupt thermal expansion. Although the pattern quality is divided into partial removal, complete removal, and ITO film damage, the ITO film surface is slightly melted even at the complete removal condition. Optimal process window, which results in complete removal of Ta_0.1W_0.9O_x thin film without ablation damage in the ITO layer, have been established. From this study, it is found that focusing lens with longer focal length is preferable for damage-free pattern generation and shorter machining time.     

XPS studies of short pulse laser interaction with copper

The effect of laser ablation on copper foil irradiated by a short 30 ns laser pulse was investigated by X-ray photoelectron spectroscopy. The laser fluence was varied from 8 to 16.5 J/cm² and the velocity of the laser beam from 10 to 100 mm/s. This range of laser fluence is characterized by a different intensity of laser ablation. The experiments were done in two kinds of ambient atmosphere: air and argon jet gas.The chemical state and composition of the irradiated copper surface were determined using the modified Auger parameter (α′) and O/Cu intensity ratio. The ablation atmosphere was found to influence the size and chemical state of the copper particles deposited from the vapor plume. During irradiation in air atmosphere the copper nanoparticles react with oxygen and water vapor from the air and are deposited in the form of a CuO and Cu(OH)₂ thin film. In argon atmosphere the processed copper surface is oxidized after exposure to air.     

Nanostructures on SiC surface created by laser microablation

Silicon carbide (SiC), as it is well-known, is inaccessible to usual methods of technological processing. Consequently, it is important to search for alternative technologies of processing SiC, including laser processing, and to study the accompanying physical processes. The work deals with the investigation of pulsed laser radiation influence on the surface of 6H-SiC crystal. The calculated temperature profile of SiC under laser irradiation is shown. Structural changes in surface and near-surface layers of SiC were studied by atomic force microscopy images, photoluminescence, Raman spectra and field emission current-voltage characteristics of initial and irradiated surfaces. It is shown that the cone-shaped nanostructures with typical dimension of 100-200 nm height and 5-10 nm width at the edge are formed on SiC surface under nitrogen laser exposure (λ = 0.337 μm, t_p = 7 ns, E_p = 1.5 mJ). The average values of threshold energy density 〈W_thn〉 at which formation of nanostructures starts on the 0 0 0 1 and surfaces of n-type 6H-SiC(N), nitrogen concentration n_N ≅ 2 × 10¹⁸ cm⁻³, are determined to be 3.5 J/cm² and 3.0 J/cm², respectively. The field emission appeared only after laser irradiation of the surface at threshold voltage of 1000 V at currents from 0.7 μA to 0.7 mA. The main role of the thermogradient effect in the processes of mass transfer in prior to ablation stages of nanostructure formation under UV laser irradiation (LI) was determined. We ascertained that the residual tensile stresses appear on SiC surface as a result of laser microablation. The nanostructures obtained could be applied in the field of sensor and emitting extreme electronic devices.     

Femtosecond pulsed laser ablation of diamond-like carbon films on silicon

Femtosecond pulsed laser ablation (τ = 120 fs, λ = 800 nm, repetition rate = 1 kHz) of thin diamond-like carbon (DLC) films on silicon was conducted in air using a direct focusing technique for estimating ablation threshold and investigating the influence of ablation parameter on the morphological features of ablated regions. The single-pulse ablation threshold estimated by two different methods were ?_th(1) = 2.43 and 2.51 J/cm². The morphological changes were evaluated by means of scanning electron microscopy. A comparison with picosecond pulsed laser ablation shows lower threshold and reduced collateral thermal damage.     

Study of cerium doped magnetite (Fe3O4:Ce)/PMMA nanocomposites

The paper presents the synthesis and properties of polymer nanocomposite material based on cerium doped magnetite (Fe₃O₄) as filler material and poly methyl methacrylate (PMMA) as host matrix. The magnetite (Fe₃O₄) particles were synthesized by co-precipitation route using stable ferrous and ferric salts with ammonium hydroxide as precipitating agent. Further, they doped by cerium oxide (CeO₂) non-stoichiometrically. The composite material was fabricated by solvent evaporation method. Here 2.4 GHz microwaves were used to study the effect of microwaves heating on polymerization. The phase and crystal structure is determined by X-ray diffraction (XRD). The average crystallite size of the composites varies from 28 to 35 nm. The chemical structure is confirmed by Fourier transform infrared (FTIR) spectroscopy. The magnetic and thermal properties are investigated by vibrating sample magnetometer (VSM) and differential scanning calorimetry (DSC). The thermal study shows that the microwave heated samples possess higher glass transition temperature (T_g). The magnetic results suggest that coercivity (H_C) and squareness (M_r/M_s) of the loop increases with increasing doping percent of cerium.     

Analyses of surface coloration on TiO2 film irradiated with excimer laser

TiO₂ film of around 850 nm in thickness was deposited on a soda-lime glass by PVD sputtering and irradiated using one pulse of krypton-fluorine (KrF) excimer laser (wavelength of 248 nm and pulse duration of 25 ns) with varying fluence. The color of the irradiated area became darker with increasing laser fluence. Irradiated surfaces were characterized using optical microscopy, scanning electron microscopy, Raman spectroscopy and atomic force microscopy. Surface undergoes thermal annealing at low laser fluence of 400 and 590 mJ/cm². Microcracks at medium laser fluence of 1000 mJ/cm² are attributed to surface melting and solidification. Hydrodynamic ablation is proposed to explain the formation of micropores and networks at higher laser fluence of 1100 and 1200 mJ/cm². The darkening effect is explained in terms of trapping of light in the surface defects formed rather than anatase to rutile phase transformation as reported by others. Controlled darkening of TiO₂ film might be used for adjustable filters.     

Low field magneto-transport in LBSMO–PMMA composite

The low field magneto-transport has been measured as a function of temperature in the range 77–300 K and magnetic field; H?3.6 kOe for La_0.7Ba_0.2Sr_0.1MnO₃ (LBSMO)–x wt% PMMA composites where x=0, 2, 6 and 10. The X-ray diffraction (XRD) study reveals that no structural modification has occurred in the LBSMO in the composite. Scanning electron microscopy (SEM) investigation shows PMMA getting dispersed through the sample volume and some LBSMO grains appear to be coated with the polymer. The metal-like transition observed at ∼150 K in the virgin LBSMO sample disappears in the composite samples and the resistance shows an increase of about three orders of magnitude as the polymer concentration is increased to 10 wt%. Despite this huge increase in the resistance, the low field magneto-resistance (LFMR) shows an enhancement although smaller than the values commonly observed for other manganite-polymer composite systems. Spin polarized tunneling that causes LFMR seems to be enhanced in the composites.     

Dielectric behavior and charge transport in polyaniline nanofiber reinforced PMMA composites

PAni nanofibers synthesized by interfacial polymerization were reinforced in the PMMA matrix in different weight ratios. Randomly oriented polyaniline nanofibers were observed in the TEM image with diameter ranging from 20 to 30 nm. The SEM revealed the microstructure of the fiber reinforced composites showing better connectivity. The XRD spectra of the composites showed peaks at 2θ=17.05°, 20.3°, 27.15° and 30.05° that were indexed in a pseudo-orthorhombic unit cell. The dielectric constant measured over a frequency range of 42 Hz-1 MHz and in the temperature range of 303-373 K showed dependence upon frequency, temperature and concentration of the conducting nanofibers in the composites. The ac conductivity (σ_ac) was interpreted as a power law of frequency. The frequency exponent s was found to lie in the range from 0.4 to 0.65 and decreased with the increase in temperature, which suggested that correlated barrier hopping (CBH) was the dominant charge transport mechanism. Existence of polarons as major charge carriers was confirmed by the low values of polaron binding energy (W_M). Decrease in the values of density of states N(E_F) with the increase in PAni nanofiber concentration indicated increased delocalization of electronic states in the band gap causing the increase in ac conductivity.     

43 W picosecond laser and second-harmonic generation experiment

Combining the advantages of diode-end-pumped Nd: YVO₄ and diode-side-pumped Nd: YAG amplifiers, a high average power and high beam quality picosecond laser is designed. The system delivers a picosecond laser with average power of 43.4 W and good beam quality of M² < 1.7. By focusing the high power picosecond laser in LBO crystal, 532 nm green laser with maximal power of 20.8 W is generated and the conversion efficiency of second-harmonic generation reaches 56.4% when 17.7 W green laser obtained from the fundamental frequency laser with power of 31.4 W and beam quality of M² < 1.25.     

Surface roughness analysis and improvement of PMMA-based microfluidic chip chambers by CO2 laser cutting

For the microfluidic chip, the surface roughness of the chamber sidewall is an important parameter in estimating its quality. In this work, the chambers of the polymethyl methacrylate (PMMA)-based microfluidic chip were fabricated by CO₂ laser cutting, and then the surface roughness of the sections cut using different laser parameters and ambient temperature was studied by a non-contact 3D surface profiler. Our observation shows that the surface roughness results primarily from the residues on the laser-cut edge, which are produced by the bubbles bursting. To reduce the surface roughness of the cut section, a new approach is proposed, that is preheating the PMMA sheet to a suitable ambient temperature during laser processing. The results indicate that at a preheat temperature of 70-90 °C, the surface roughness resulting from the cut would be reduced. In our experiment, the best result was that the arithmetical mean roughness is R_a = 100.86 nm when the PMMA sheet was heated to 85 °C.     

Photosensitivity and grating development in trans-4-stilbenemethanol-doped poly(methyl methacrylate) materials

This paper reports the photosensitivity of poly(methyl methacrylate) (PMMA) and its copolymer doped with trans-4-stilbenemethanol. UV irradiation of the doped-PMMA at 325 nm induced the trans- to cis-isomerization of the dopant. This process was confirmed by ¹H NMR spectra of trans-4-stilbenemethanol in CDCL₃ solvent before and after irradiation. The isomerization can be initiated by the irradiation with an intensity of 0.62 mW/cm². Photo-induced refractive index change of −0.0024 was obtained when a PMMA copolymer film doped with 5.1 wt% dopant was exposed to 325 nm light. Lorentz-Lorenz equation was used to estimate the refractive index of a trans-4-stilbenemethanol-PMMA composite and a trans-4-stilbenemethanol-PMMA copolymer composite from the mole refraction and van der Waals volume of each component. A slight elevation of molecular packing coefficient (K) for PMMA and its copolymer containing the dopant implies a denser aggregation as compared to the polymer without the dopant. Long period gratings were created in doped-PMMA films and doped-PMMA copolymer fibers using amplitude mask technique. Gratings were confirmed by microscopic observation and diffraction patterns.     

Removal of doped poly(methylmetacrylate) from tungsten and titanium substrates by femto- and nanosecond laser cleaning

The influence of different laser pulse lengths on the removal of a polymer layer from metal substrates was investigated. As model systems, doped poly(methylmetacrylate) (PMMA) on titanium and tungsten substrates were selected.The ablation threshold and irradiation spot morphology of titanium and tungsten were compared for femtosecond (fs) and nanosecond (ns) laser irradiation and different pulse numbers. Nanosecond laser treatment resulted in a non-homogeneous surface morphology for both titanium and tungsten substrates. Femtosecond irradiation of tungsten revealed a homogeneous ablation spot with little changes in the surface morphology. For titanium, the formation of columnar structures within the irradiation spot was observed.Two different dopant concentrations were used for PMMA to achieve an equal linear absorption coefficient for the femto- and nanosecond laser wavelengths of 790 and 1064 nm. The best results were achieved for the removal of doped PMMA by femtosecond laser irradiation, where only a minimal modification of the metal surface was detected. In the case of nanosecond laser exposure, a pronounced change of the structure was observed, suggesting that damage-free cleaning of the selected metal may only be possible using femtosecond laser pulses. Different experimental parameters, such as laser fluence, pulse repetition rate and sample speed were also investigated to optimize the cleaning quality of doped PMMA from tungsten substrates with femtosecond laser pulses.