Transient pressure induced by laser ablation of toluene, a highly laser-absorbing liquid

Transient processes of laser ablation of a highly laser-absorbing liquid, toluene, were investigated by directly measuring (by using a fast-response pressure gauge) the transient pressure caused by toluene ablation under KrF laser irradiation . The results were compared with time-resolved images . The peak pressure P due to a shock wave decreased slowly with increasing distance d for d=100–1000 m:Pd^-0.33. By extrapolating P to d=8.9 m, the optical penetration depth of toluene at =248 nm, the estimated initial pressure due to toluene ablation was 65 MPa at 1.0 J cm^-2 pulse^-1. The estimated initial pressure increased linearly with the fluence. These results help clarify the mechanism of laser-induced backside wet etching. PACS 79.20.Ds; 47.40.Nm; 47.55.Bx; 81.65.Cf     

Microstructuring of fused silica by laser-induced backside wet etching using picosecond laser pulses

The laser-induced backside wet etching (LIBWE) is an advanced laser processing method used for structuring transparent materials. LIBWE with nanosecond laser pulses has been successfully demonstrated for various materials, e.g. oxides (fused silica, sapphire) or fluorides (CaF₂, MgF₂), and applied for the fabrication of microstructures. In the present study, LIBWE of fused silica with mode-locked picosecond (t_p = 10 ps) lasers at UV wavelengths (λ₁ = 355 nm and λ₂ = 266 nm) using a (pyrene) toluene solution was demonstrated for the first time. The influence of the experimental parameters, such as laser fluence, pulse number, and absorbing liquid, on the etch rate and the resulting surface morphology were investigated. The etch rate grew linearly with the laser fluence in the low and in the high fluence range with different slopes. Incubation at low pulse numbers as well as a nearly constant etch rate after a specific pulse number for example were observed. Additionally, the etch rate depended on the absorbing liquid used; whereas the higher absorption of the admixture of pyrene in the used toluene enhances the etch rate and decreases the threshold fluence. With a λ₁ = 266 nm laser set-up, an exceptionally smooth surface in the etch pits was achieved. For both wavelengths (λ₁ = 266 nm and λ₂ = 355 nm), LIPSS (laser-induced periodic surface structures) formation was observed, especially at laser fluences near the thresholds of 170 and 120 mJ/cm², respectively.     

Micromachining of quartz crystal with excimer lasers by laser-induced backside wet etching

We fabricated a well-defined pattern of lines and spaces on the surface of a quartz crystal plate (c-SiO₂) with micron-sized features, using laser-induced backside wet etching (LIBWE). The line patterns obtained using LIBWE showed a high aspect ratio of about 3. The etch rates of fused silica (a-SiO₂) ranged from 5 to 25 nm/pulse with KrF laser irradiation from 0.4-1.3 J/cm². Threshold fluences for a-SiO₂ and c-SiO₂ were 0.23 and 0.34 J/cm², respectively. The single-pulse etch depth was not affected by the repetition rates of laser pulses from 1-50 Hz.     

Effects of halogenated organic solvents on laser-induced backside wet etching of fused silica

Laser-induced backside wet etching of fused silica using a solution of pyrene dissolved in halogenated and non-halogenated solvents is presented. A significant influence of the solvent used on the etch rate and the etched surface appearance was ascertained. The etching of uniform and smooth surfaces with rates of ∼0.1 nm/pulse for laser fluences below 500 mJ/cm² is observed only for halogenated solvents. Furthermore, reduced threshold fluences, only small incubation effects, and a constant etch rate in dependence on the pulse number were found. The experimental data suggest an additional etch process at low laser fluences characterized by the very low etch rate and the smooth etching observed only with halogen-containing solvents. The generation of halogen radicals/compounds close to the heated surface due to the decomposition of the solvent causing the attack of the surface seems the most probable mechanism. PACS 81.65.Cf; 81.05.Kf; 79.20.Ds; 61.80.Ba; 42.55.Lt; 68.45.Da     

Surface plasmon scattering on polymer-bimetal layer covered fused silica gratings generated by laser induced backside wet etching

Large amplitude fused silica gratings are prepared by combining the UV laser induced backside wet etching technique (LIBWE) and the two-beam interference method. The periodic patterning of fused silica surfaces is realized by s-polarized fourth harmonic beams of a Nd:YAG laser, applying saturated solution of naphthalene in methyl-methacrylate as liquid absorber. Atomic force microscopy is utilized to analyze how the modulation amplitude of the grating can be controlled by the fluence and number of laser pulses. Three types of plasmonic structures are prepared by a bottom-up method, post-evaporating the fused silica gratings by gold-silver bimetal layers, spin-coating the metal structures by thin polycarbonate films, and irradiating the multilayers by UV laser. The effect of the bimetal and polymer-coated bimetal gratings on the surface plasmon resonance is investigated in a modified Kretschmann arrangement allowing polar and azimuthal angle scans. It is demonstrated experimentally that scattering on rotated gratings results in additional minima on the resonance curves of plasmons excited by second harmonic beam of a continuous Nd:YAG laser. The azimuthal angle dependence proves that these additional minima originate from back-scattering. The analogous reflectivity minima were obtained by scattering matrix method calculations realized taking modulation depths measured on bimetal gratings into account.     

Fabrication of 550 nm gratings in fused silica by laser induced backside wet etching technique

A series of 550 nm spacing gratings were fabricated in fused silica by laser induced backside wet etching (LIBWE) method using the fourth harmonic of a Q-switched Nd:YAG laser (wavelength: λ = 266 nm; pulse duration: FWHM = 10 ns). During these experiments we used a traditional two-beam interference method: the spatially filtered laser beam was split into two parts, which were interfered at a certain incident angle (2θ = 28°) on the backside surface of the fused silica plate contacting with the liquid absorber (saturated solution of naphthalene-methyl-methacrylate c = 1.85 mol/dm³). We studied the dependence of the quality and the modulation depth of the prepared gratings on the applied laser fluence and the number of laser pulses. The surface of the etched gratings was characterized by atomic force microscope (AFM). The maximum modulation depth was found to be 180-200 nm. Our results proved that the LIBWE procedure is suitable for production of submicrometer sized structures in transparent materials.     

Laser-induced backside wet etching of fluoride and sapphire using picosecond laser pulses

Laser-induced backside wet etching (LIBWE) is a promising process for microstructuring of rigid chemical resistant and inert transparent materials. LIBWE with nanosecond laser pulses has been successfully demonstrated in a number of studies. LIBWE in a time scale of femtosecond and picosecond pulse durations has been investigated only in a few studies and just on fused silica. In the present study LIBWE of fluorides (CaF₂, MgF₂) and sapphire with a mode-locked picosecond (t _p=10 ps) laser at a UV wavelength of λ=355 nm using toluene as absorbing liquid has been demonstrated. The influence of the laser fluence and the pulse number on the etching rate and the achieved surface morphology was investigated. The etching rate grows linearly with the laser fluence in the low and high-fluence ranges with different slopes. The achieved etching rates for CaF₂ and for sapphire were in the same range. Contrary to CaF₂ and sapphire the etching rates of MgF₂ were one magnitude less. For backside etching on sapphire at high fluences smooth surfaces and at low fluences ripples pattern were found, whereas fluoride surfaces showed a trend towards crack formation.     

104 nm period grating fabrication in fused silica by immersion two-beam interferometric laser induced backside wet etching technique

A substantial extension of the method of two-beam interferometric laser induced backside wet etching (TWIN-LIBWE), the immersion TWIN-LIBWE, is used to fabricate fused silica gratings with a 104 nm period. The spatially filtered fourth harmonic of Nd:YAG laser (λ=266 nm, τ_FWHM=8 ns) pulses were split into two parts which then interfered at the backside of the fused silica target in contact with a liquid absorber (naphthalene methyl methacrylate saturated solution with a concentration of 1.85 mol/dm³). The hypotenuse of a rectangular fused silica prism is attached to the fused silica target with the use of distilled water as the immersion liquid. On steering the beams through the sides of the prisms, the angle between the two laser beams has been substantially increased. The resulting period of 104 nm is the minimal grating constant achievable under such experimental conditions and, to our knowledge, the smallest laser generated grating period in fused silica at present. PACS 42.62; 42.79; 81.65     

The influence of laser-induced surface modifications on the backside etching process

Spectroscopic measurements in the UV/VIS region show reduced transmission through laser-induced backside wet etching (LIBWE) of fused silica. Absorption coefficients of up to 10⁵ cm⁻¹ were calculated from the transmission measurements for a solid surface layer of about 50 nm. The temperatures near the interface caused by laser pulse absorption, which were analytically calculated using a new thermal model considering interface and liquid volume absorption, can reach 10⁴ K at typical laser fluences. The high absorption coefficients and the extreme temperatures give evidence for an ablation-like process that is involved in the LIBWE process causing the etching of the modified near-surface region. The confinement of the ablation/etching process to the modified near-surface material region can account for the low etch rates observed in comparison to front-side ablation.     

In situ reflectivity investigations of solid/liquid interface during laser backside etching

In situ reflectivity measurements of the solid/liquid interface with a pump-probe setup were performed during laser-induced backside wet etching (LIBWE) of fused silica with KrF excimer laser using toluene as absorbing liquid. The intensity, the temporal shape, and the duration of the reflected light measured in dependence on the laser fluence are discussed referring to the surface modification and the bubble formation.The vaporisation of the superheated liquid at the solid interface causes a considerable increase of the reflectivity and gives information about the bubble lifetime. The alterations of the reflectivity after bubbles collapse can be explained with the changed optical properties due to surface modifications of the solid surface. Comparative studies of the reflectivity at different times and the etch rate behaviour in dependence on the laser fluence show that the in situ measured surface modification begins just at the etch threshold fluence and correlates further with etch rate behaviour and the etched surface appearance. The already observed surface modification at LIBWE due to a carbon deposition and structural changes of the near surface region are approved by the changes of the interface reflectivity and emphasizes the importance of the modified surface region in the laser-induced backside wet etching process.     

Influence on the laser induced backside dry etching of thickness and material of the absorber, laser spot size and multipulse irradiation

Laser induced backside dry etching method (LIBDE) was developed - analogously to the well-known laser induced backside wet etching (LIBWE) technique - for the micromachining of transparent materials. In this procedure, the absorbing liquid applied during LIBWE was replaced with solid metal layers. Fused silica plates were used as transparent targets. These were coated with 15-120 nm thick layers of different metals (silver, aluminium and copper). The absorbing films were irradiated by a nanosecond KrF excimer laser beam through the quartz plate. The applied fluence was varied in the 150-2000 mJ/cm² range, while the irradiated area was between 0.35 and 3.6 mm². At fluences above the threshold values, it was found that the metal layers were removed from the irradiated spots and the fused silica was etched at the same time. In our experiments, we investigated the dependence of the main parameters (etch rate and threshold) of LIBDE on the absorption of the different metal layers (silver, copper, aluminium), on the size of the irradiated area, on the film thickness and on the number of processing laser pulses.     

Laser ablation of liquid surface in air induced by laser irradiation through liquid medium

The pulse laser ablation of a liquid surface in air when induced by laser irradiation through a liquid medium has been experimentally investigated. A supersonic liquid jet is observed at the liquid–air interface. The liquid surface layer is driven by a plasma plume that is produced by laser ablation at the layer, resulting in a liquid jet. This phenomenon occurs only when an Nd:YAG laser pulse (wavelength: 1064 nm) is focused from the liquid onto air at a low fluence of 20 J/cm². In this case, as Fresnel’s law shows, the incident and reflected electric fields near the liquid surface layer are superposed constructively. In contrast, when the incident laser is focused from air onto the liquid, a liquid jet is produced only at an extremely high fluence, several times larger than that in the former case. The similarities and differences in the liquid jets and atomization processes are studied for several liquid samples, including water, ethanol, and vacuum oil. The laser ablation of the liquid surface is found to depend on the incident laser energy and laser fluence. A pulse laser light source and high-resolution film are required to observe the detailed structure of a liquid jet.     

High-speed etching of hexagonal GaN by laser ablation and successive chemical treatment

Photostimulated direct etching of GaN has been demonstrated with extremely high etching rate up to 135 nm/pulse. The process consists of laser irradiation and ex-situhydrochloric acid treatment. Not only deep etching but also a highly planarized surface are obtained by an increase in laser fluence and the number of pulses. Seven-pulse irradiation at 1 J/cm² decreases surface average roughness (R_a) to ~2 nm from ~10 nm of the untreated sample. No deep-level emission (450-600 nm) is detected in photoluminescence measurement on the samples irradiated with laser fluences as high as 3 J/cm².     

Fabrication of grating structures on silicon carbide by femtosecond laser irradiation and wet etching

A method for fabricating deep grating structures on a silicon carbide(SiC) surface by a femtosecond laser and chemical-selective etching is developed.Periodic lines corresponding to laser-induced structure change(LISC)are formed by femtosecond laser irradiation,and then the SiC material in the LISC zone is removed by a mixed solution of hydrofluoric acid and nitric acid to form grating grooves.Grating grooves with a high-aspect ratio of approximately 25 are obtained.To obtain a small grating period,femtosecond laser exposure through a phase mask was used to fabricate grating structures with a 1.07 μm period on the surface of the SiC.     

Depth-profile investigations of triterpenoid varnishes by KrF excimer laser ablation and laser-induced breakdown spectroscopy

The ablation properties of aged triterpenoid dammar and mastic films were investigated using a Krypton Fluoride excimer laser (248 nm, 25 ns). Ablation rate variations between surface and bulk layers indicated changes of the ablation mechanisms across the depth profiles of the films. In particular, after removal of the uppermost surface varnish layers there was a reduction of the ablation step in the bulk that was in line with a significant reduction of carbon dimer emission beneath the surface layers as detected by laser-induced breakdown spectroscopy. The results are explicable by the generation of condensation, cross-linking and oxidative gradients across the depth profile of triterpenoid varnish films during the aging degradation process, which were recently quantified and established on the molecular level.     

Transient reflectivity and transmission changes during plasma formation and ablation in fused silica induced by femtosecond laser pulses

We have studied the plasma formation and ablation dynamics in fused silica upon irradiation with a single 120 fs laser pulse at 800 nm by using fs-resolved pump-probe microscope. It allows recording images of the laser-excited surface at different time delays after the arrival of the pump pulse. This way, we can extract both the temporal evolution of the surface reflectivity and transmission, at 400 nm, for different spatial positions in the spots (and thus for different local fluences) from single series of images. At fluences well above the visible ablation threshold, a fast and large increase of the reflectivity is induced by the formation of a dense free-electron plasma. The maximum reflectivity value is reached within ≈1.5 ps, while the normalized transmission decreases within ≈400 fs. The subsequent temporal evolution of both transient reflectivity and transmission are consistent with the occurrence of surface ablation. In addition, the time-resolved images reveal the existence of a free-electron plasma distribution surrounding the visible ablation crater and thus formed at local fluences below the ablation threshold. The lifetime of this sub-ablation plasma is ≈50 ps, and its maximum electron density amounts to 5.5×10²² cm⁻³.     

Nanoparticles produced by laser ablation of solids in liquid environment

A review of results on nanoparticles formation is presented under laser ablation of Ag, Au, and Ti solids targets in liquid environments (H₂O, C₂H₅OH, C₂H₄Cl₂, etc.). X-ray diffractometry (XRD), UV-Vis optical transmission spectrometry, and high-resolution transmission electron microscopy (HRTEM) characterise the nanoparticles. The morphology of nanoparticles is studied as a function of both laser fluence and nature of the liquid. The evidence of an intermediate phase of Au-Ag alloy is presented under exposure of a mixture of individual nanoparticles to laser radiation. Self-influence of the beam of a femtosecond laser is discussed under the ablation of the Ag target in liquids under Ti:sapphire laser. The factors are discussed that determine the distribution function of particle size under laser ablation. The influence of laser parameters as well as the nature on the liquid on the properties of nanoparticles is elucidated. PACS 42.62.-b; 61.46.+w; 78.66.-w     

Estimation of the capabilities of maskless micropatterning by laser-induced chemical etching

A three-dimensional mathematical model of laser-induced chemical etching of polysilicon films in chlorine atmosphere is presented. The model takes into account both photochemical and thermochemical mechanisms. A numerical solution of a simple process model and consequences for spatial resolution limits of the mask-less laser-induced chemical etching are presented.