Effect of pulse repetition rate and number of pulses in the analysis of polypropylene and high density polyethylene by nanosecond infrared laser induced breakdown spectroscopy

Pulse repetition rates and the number of laser pulses are among the most important parameters that do affect the analysis of solid materials by laser induced breakdown spectroscopy, and the knowledge of their effects is of fundamental importance for suggesting analytical strategies when dealing with laser ablation processes of polymers. In this contribution, the influence of these parameters in the ablated mass and in the features of craters was evaluated in polypropylene and high density polyethylene plates containing pigment-based PbCrO₄. Surface characterization and craters profile were carried out by perfilometry and scanning electron microscopy. Area, volume and profile of craters were obtained using Taylor Map software. A laser induced breakdown spectroscopy system consisted of a Q-Switched Nd:YAG laser (1064 nm, 5 ns) and an Echelle spectrometer equipped with ICCD detector were used. The evaluated operating conditions consisted of 10, 25 and 50 laser pulses at 1, 5 and 10 Hz, 250 mJ/pulse (85 J cm⁻²), 2 μs delay time and 6 μs integration time gate. Differences in the topographical features among craters of both polymers were observed. The decrease in the repetition rate resulted in irregular craters and formation of edges, especially in polypropylene sample. The differences in the topographical features and ablated masses were attributed to the influence of the degree of crystallinity, crystalline melting temperature and glass transition temperature in the ablation process of the high density polyethylene and polypropylene. It was also observed that the intensities of chromium and lead emission signals obtained at 10 Hz were two times higher than at 5 Hz by keeping the number of laser pulses constant.     

Fabrication of microchannels in single-crystal GaN by wet-chemical-assisted femtosecond-laser ablation

We investigated micro- and nano-fabrication of wide band-gap semiconductor gallium nitride (GaN) using a femtosecond (fs) laser. Nanoscale craters were successfully formed by wet-chemical-assisted fs-laser ablation, in which the laser beam is focused onto a single-crystal GaN substrate in a hydrochloric acid (HCl) solution. This allows efficient removal of ablation debris produced by chemical reactions during ablation, resulting in high-quality ablation. However, a two-step processing method involving irradiation by a fs-laser beam in air followed by wet etching, distorts the shape of the crater because of residual debris. The threshold fluence for wet-chemical-assisted fs-laser ablation is lower than that for fs-laser ablation in air, which is advantageous for improving fabrication resolution since it reduces thermal effects. We have fabricated craters as small as 510 nm by using a high numerical aperture (NA) objective lens with an NA of 0.73. Furthermore, we have formed three-dimensional hollow microchannels in GaN by fs-laser direct-writing in HCl solution.     

YAG laser percussion drilling of a functional multi-layer thin plate

An Au-coated Fe–Ni alloy thin plate was laser drilled by a pulsed Nd:YAG laser. The influences of laser parameters on the diameter of perforation, the outer diameter of crater and the roundness of the perforation have been investigated by employing scanning electron microscopy. The diameter of perforation increases gradually with an increase in pulse width from 0.3 to 8 ms at the fixed average laser power and frequency, and increases with an increase in average laser power from 10 to 25 W at the fixed pulse width and frequency. Some craters are found around the perforations because of the heat affecting of laser beam to the non-irradiated zone. The diametric difference of the perforation between the incident and the effluent sides is very small under the shortest pulse width of 0.3 ms. Good roundness of the perforation can be achieved at either the lowest pulse width or the lowest laser power.     

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.     

Deep subsurface optical waveguides produced by direct writing with femtosecond laser pulses in fused silica and phosphate glass

In the present work, we have analyzed the use of elliptical beam shaping along with low numerical aperture focusing optics in order to produce circular cross-section waveguides in different materials at large processing depths by direct femtosecond laser writing (100 fs, 800 nm, 1 kHz). A variable slit located before the focusing optics allows to generate a nearly elliptical beam shape and also to reduce the effective numerical aperture of the beam along the shat axis of the ellipse. The focusing optics allows to focus the beam deep inside the sample, which is translated at a constant speed transversely to the writing beam direction. The influence of several experimental parameters (energy per pulse, slit width, processing depth) on the properties of the produced waveguides has been analyzed. The influence of the intrinsic properties of the material (refractive index, composition) has been analyzed by comparing results obtained in fused silica and Er:Yb co-doped phosphate glass. The results obtained show that this approach leads to the successful production of deep subsurface (up to 7 mm) waveguides with circular cross-sections. Preliminary results using chirped pulses in the phosphate glass suggest that temporal pulse shaping can be used as an additional parameter to optimize the guided mode symmetry.     

Glass processing using the fourth harmonic of nanosecond pulse Nd:YAG laser

Ablation processing of borosilicate glass was carried out using the fourth harmonic of the Q-switch Nd:YAG laser. The dependency of the ablation depth on irradiation pulse energy density and the dependency of the ablation depth on irradiation spot size were investigated. The average ablation depth increased with an increase in irradiation pulse energy density. When the irradiation pulse energy density was the same, the ablation depth of the focused beam with a large spot diameter was deeper than that of the focused beam with a small spot diameter. To shorten the processing time, an increase in the irradiation pulse energy density and use of a large spot size focused beam are effective. Using area scanning together with line scanning, a rectangular through hole (sub-mm size) without cracks or chips was formed in borosilicate glass of 140 μm in thickness. PACS 52.38.Mf; 42.70.Ce; 42.62.Cf     

Line patterning with large refractive index changes in the deep inside of glass by nanosecond pulsed YAG laser irradiation

Nanosecond (∼100 ns) pulsed (10 Hz) Nd:YAG laser operating at the wavelength (λ) of 1064 nm with pulse energies of 0.16-1.24 mJ/cm² has irradiated 10Sm₂O₃·40BaO·50B₂O₃ glass. It is demonstrated for the first time that the structural modification resulting the large decease (∼3.5%) in the refractive index is induced by the irradiation of YAG laser with λ=1064 nm. The lines with refractive index changes are written in the deep inside of 100-1000 μm depths by scanning laser. The line width is 1-13 μm, depending on laser pulse energy and focused beam position. It is proposed that the samarium atom heat processing is a novel technique for inducing structural modification (refractive index change) in the deep interior of glass.     

355 nm nanosecond pulsed Nd:YAG laser profile measurement, metal thin film ablation and thermal simulation

Laser ablation of nickel, gold and copper thin film on glass substrates has been investigated using a nanosecond pulsed Nd:YAG laser operating at 355 nm in air with a Gaussian intensity profile. The exact beam profile was measured through mechanical scanning with a photodiode. A small beam defect was observed, which can affect the machining performance at higher pulse energies. The ablation thresholds of the films were calculated from the crater diameter values. The effect of the pulse repetition rate and the film thickness was also studied. At high pulse repetition rates heat accumulation was observed and the ablation threshold decreased with the film thickness. Both cases resulted in higher diameters.     

Effect of spot size on cone formation in a XeCl laser ablation of polyethersulfone films

Radiation from the UV excimer lasers, with the fluence above the ablation threshold, can etch the polymer surfaces by photoablation. In some cases different microstructures may appear on the surface during the laser ablation. In this paper the effect of the laser spot size on the cone formation on polyethersulfone films has been investigated. The experiments have been performed with a XeCl laser at the wavelength of 308 nm and at the fluences of 70 and 100 mJ/cm² at air. For the investigation of the effect of the laser spot size on cone formation, the samples were irradiated at two different laser spot sizes of w₁ and w₂ = 0.1 w₁. The morphology of the processed surface was studied by scanning electron microscopy (SEM). It has shown that the shape, size and density of cones change with the change of the laser spot size. Also, the number of pulses and the pulse repetition rate which are needed for threshold of cone formation are affected by the laser beam spot size on the surface.     

Formation of periodic surface nanostructures on Ti:Al2O3 crystals using femtosecond laser pulses

Periodic surface nanostructures are observed on Ti³⁺:Al₂O₃ single crystals that have been irradiated by a single focused beam from a femtosecond pulsed laser (wavelength: 800 nm; pulse duration: 130 and 152 fs). Atomic force microscopy images of single-ablated zones and modified structures created by fixing and translating samples through the focal region of a linearly polarized laser beam reveal self-organized periodic surface nanostructures (ripples) with a subwavelength spacing, which are oriented perpendicular to the electric-field vector of the laser beam. The period of the subwavelength ripples obtained by linearly polarized laser irradiation varies from ∼λ/5 to 2λ/5 (λ: incident laser wavelength) depending on the laser pulse energy. This phenomenon can be explained by assuming that the incident light field interferes with the electric field of electron plasma waves propagating inside the material; this interference periodically modulates the electron plasma density and modifies the surface ablation. In addition, for the first time, we observe screw-shaped nanostructures in the focal spot of circularly polarized beam irradiation. The morphology of these nanostructures appears to reflect the circular polarization of the laser light.     

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.     

Plasma-mediated ablation of biofilm contamination

Ultra-short pulsed laser removal of thin biofilm contamination on different substrates has been conducted via the use of plasma-mediated ablation. The biofilms were formed using sheep whole blood. The ablation was generated using a 1.2 ps ultra-short pulsed laser with wavelength centered at 1552 nm. The blood contamination was transformed into plasma and collected with a vacuum system. The single line ablation features have been measured. The ablation thresholds of blood contamination and bare substrates were determined. It is found that the ablation threshold of the blood contamination is lower than those of the beneath substrates including the glass slide, PDMS, and human dermal tissues. The ablation effects of different laser parameters (pulse overlap rate and pulse energy) were studied and ablation efficiency was measured. Proper ablation parameters were found to efficiently remove contamination with maximum efficiency and without damage to the substrate surface for the current laser system. Complete removal of blood contaminant from the glass substrate surface and freeze-dried dermis tissue surface was demonstrated by the USP laser ablation with repeated area scanning. No obvious thermal damage was found in the decontaminated glass and tissue samples.     

Gain-saturated Ni-like antimony laser at 11.4 nm in grazing-incidence pumping geometry

We report on gain-saturated operation of the 4d → 4p, J = 0-1, 11.4 nm soft-X-ray laser line in Ni-like antimony (Sb) at a pump energy of only 2.5 J. The driving laser used was a 1054 nm Nd:glass CPA laser system with a pulse duration of 7 ps (FWHM). The pump beam was focused with a tilted on-axis parabolic mirror in a grazing-incidence (GRIP) pumping configuration at an incidence angle of 45°. A fraction of 2.8% of the pump energy (∼70 mJ) was used for the prepulse, which was propagated along the same beam line as the main pulse and arrived at the target 4.4 ns before the main pulse.     

Laser fluence, repetition rate and pulse duration effects on paint ablation

The efficiency (mm³/(J pulse)) of laser ablation of paint was investigated with nanosecond pulsed Nd:YAG lasers (λ = 532 nm) as a function of the following laser beam parameters: pulse repetition rate (1-10,000 Hz), laser fluence (0.1-5 J/cm²) and pulse duration (5 ns and 100 ns). In our study, the best ablation efficiency (η ≅ 0.3 mm³/J) was obtained with the highest repetition rate (10 kHz) at the fluence F = 1.5 J/cm². This ablation efficiency can be associated with heat accumulation at high repetition rate, which leads to the ablation threshold decrease. Despite the low thermal diffusivity and the low optical absorption of the paint (thermal confinement regime), the ablation threshold fluence was found to depend on the pulse duration. At high laser fluence, the ablation efficiency was lower for 5 ns pulse duration than for the one of 100 ns. This difference in efficiency is probably due to a high absorption of the laser beam by the ejected matter or the plasma at high laser intensity. Accumulation of particles at high repetition rate laser ablation and surface shielding was studied by high speed imaging.     

Analysis of materials modifications caused by UV laser micro drilling of via holes in AlGaN/GaN transistors on SiC

Pulsed UV laser drilling can be applied to fabricate vertical electrical interconnects (vias) for AlGaN/GaN high electron mobility transistor devices on single-crystalline silicon carbide (SiC) substrate. Through-wafer micro holes with a diameter of 50-100 μm were formed in 400 μm thick bulk 4H-SiC by a frequency-tripled solid-state laser (355 nm) with a pulse width of ≤30 ns and a focal spot size of ∼15 μm. The impact of laser machining on the material system in the vicinity of micro holes was investigated by means of micro-Raman spectroscopy and transmission electron microscopy. After removing the loosely deposited debris by etching in buffered hydrofluoric acid, a layer of <4 μm resolidified material remains at the side walls of the holes. The thickness of the resolidified layer depends on the vertical distance to the hole entry as observed by scanning electron microscopy. Micro-Raman spectra indicate a change of internal strain due to laser drilling and evidence the formation of nanocrystalline silicon (Si). Microstructure analysis of the vias’ side walls using cross sectional TEM reveals altered degree of crystallinity in SiC. Layers of heavily disturbed SiC, and nanocrystalline Si are formed by laser irradiation. The layers are separated by 50-100 nm thick interface regions. No evidence of extended defects, micro cracking or crystal damage was found beneath the resolidified layer. The precision of UV laser micro ablation of SiC using nanosecond pulses is not limited by laser-induced extended crystal defects.     

Crater geometry characterization of Al targets irradiated by single pulse and pulse trains of Nd:YAG laser in ambient air and water

High intensities laser pulses are capable to generate a crater when irradiating metal targets. In such condition, after each irradiation significant ablation occurs on the target surface and as a result a crater is formed. The crater characterization is very important specifically for some applications such as micromachining. In this paper, the crater formation in metal targets was studied experimentally. The planar aluminum 5052 targets were irradiated by frequency doubled (532 nm), Q-switched Nd:YAG (∼6 ns) laser beam in ambient air and distilled water. A crater was produced after each irradiation and it was characterized by an optical microscope. Different laser intensities as well as pulse trains were applied for crater formation. The effects of laser characteristics in crater geometry were examined. The depth of the craters was measured by optical microscope and the diameter (width) was characterized by processing of the crater image. The results were explained in terms of ablation threshold and plasma shielding. The results show that the crater geometry extremely depends on the laser pulse intensity, the number of laser pulses, and ambient.     

High-energy, spatially flat-top green pump laser by beam homogenization for petawatt scale Ti:sapphire laser systems

We have demonstrated that we can homogenize the spatial profile of a high-energy green laser pulse used for pumping a petawatt scale Ti:sapphire amplifier. The second harmonic of a high-energy, large aperture Nd:glass laser system generates laser emission at a green wavelength with 75 J single pulse energy. Using a diffractive optical element for beam homogenization, we have obtained a highly spatially uniform flat-top second harmonic profile.     

Morphology of ablation craters generated by fs laser pulses in LiNbO3

The surface morphology of the ablation craters generated in LiNbO₃ by 130 fs laser pulses at 800 nm has been investigated by AFM/SNOM microscopy. The single pulse fluence corresponding to the ablation threshold has been estimated to be ≈1.8 J/cm².A complex structure including random cone-shaped protrusions is observed inside the ablated crater. The scale of the protrusion spacing is in the submicron range and the heights are typically of a few tens of nanometers. At and outside the crater rim a novel quasi-periodic wave-like topography pattern is observed in both types of microscopy techniques. The average wavelength, that is slightly dependent on pulse fluence, is (500-800 nm) comparable to the light wavelength. This novel topography feature keeps a close similarity with a Fresnel diffraction pattern by an absorbing circular obstacle or impact wave pattern produced by a combination of heat and shock wave (resemble that of impact crater). It is proposed that the obstacle is associated to the strongly nonlinear multiphoton absorption at the peak of the pulse profile. The energy deposited by nonlinear absorption of such profile causes ablation of both the crater and the rippled structure.     

Enhancement of resolution and quality of nano-hole structure on GaN substrates using the second-harmonic beam of near-infrared femtosecond laser

By using a second harmonic of near infrared femtosecond (fs) laser (λ=387 nm, 150 fs) with high NA objective lens, fabrication resolution has been greatly improved in nano-fabrication of wide band-gap semiconductor gallium nitride (GaN). We have carried out a wet-chemical-assisted fs laser ablation method, in which the laser beam is focused onto a single-crystal GaN substrate immersed in a concentrated hydrochloric (HCl) acid solution. A two-step processing involving irradiation with a fs laser beam in air followed by wet chemical treatment is also performed for comparison. In the wet-chemical-assisted ablation, theoretical diameters of ablation craters are calculated as a function of pulse energy by assuming that the reaction is based on two-photon absorption. In lower energy, the calculated curve is close to the experimental value, while the actual measured diameters in the region of higher energy are larger than calculated values. In the condition of the highest fabrication resolution, we obtained ablation craters smaller than 200 nm at full width at half maximum. We have also demonstrated the fabrication of two-dimensional (2D) periodic nanostructures on surface of a GaN substrate using the second harmonic single fs-laser pulse. Uniform ablation craters with the size as small as 410 nm in diameter are arranged with a periodicity of 1 μm. Such structures are applicable to 2D photonic crystals which improve the light extraction efficiency for blue LEDs in the near future.     

Femtosecond laser induced submicrometer structures on the ablation crater walls of II-VI semiconductors in water

Femtosecond laser ablations (100 fs, 800 nm, 0.2 mJ/pulse) were performed to produce craters on CdS, ZnS:Cu and ZnSe wafers in water. On the surface of the crater walls, a variety of submicrostructural formations were presented, such as the ripples and network structures for CdS, the subwavelength ripples and columnar structures for ZnS:Cu, even the regular cubic-shaped submicron rods for ZnSe. Based on the field-emission scanning electron microscope (FE-SEM) study of the different characteristic surface morphologies, the possible formation mechanisms were discussed correspondingly. For example, two distinct mechanisms are contributing to the different styles of ripples formed on CdS and ZnS:Cu. The former is the interference effects between the incoming laser beam and scattered surface wave, while the latter is the self-organization structure formation. In addition, the re-crystallization of the water-confined hot plasma would play an important role in the formation of ZnS:Cu column structures and ZnSe rods.