Dopant-induced excimer laser ablation of Poly(tetrafluoroethylene)

Poly(tetrafluoroethylene) (PTFE) does not exhibit excimer laser etching behavior at conventional, e.g., single photon absorption, emissions of 193, 248, and 308 nm, due to the lack of polymer/photon interaction. This is not surprising since the electronic transitions available to the PTFE molecule are high energy and thus require short wavelength the radiation However, by incorporating a small quantity of material into the non-absorbing fluoropolymer matrix that interacts strongly with the emitted laser energy, e.g., a dopant, successful ablation, both in terms of etch rate and structuring quality occurs. Specifically, excimer laser ablation of PTFE films containing 5, 10, and 15% polyimide (wt/wt) as a dopant was achieved at 308 nm in a fluence range of 1 to 12 J/cm². Ablation rates for the materials increased with increasing fluence and, at the polyimide levels investigated, varied inversely with dopant concentration. All compositions exhibited excellent structuring quality.     

Shock waves generated by confined XeCl excimer laser ablation of polyimide

We investigate shock waves generated by excimer laser ablation of sheet polyimide confined in water. The velocities of the ablation-induced pressure waves in the water are determined by an optical probe system. We measure supersonic velocities up to a few hundred microns away from the irradiated surface, indicating the formation of shock waves. We use these velocities to calculate the corresponding pressures. They are already in the kbar range at fluences comparable to the threshold of ablation. The shock pressure varies as the square root of the incident laser fluence, a behavior that is explained by the rapid heating of the confined gaseous products of ablation.The initially planar shock waves propagate, become spherical, and decay within a few hundred microns in the surrounding water to acoustic waves. During spherical expansion the shock pressure drops as the inverse of the square of the propagation distance.The shock waves generated may be relevant in explaining photoacoustic damage observed in biological tissue after excimer-ablation at corresponding irradiances. They may also be important in material processing applications of excimer laser ablation of polymers as they can lead to plastic deformation.     

KrF-laser ablation of polyurethane

Polyurethane can be effectively and cleanly ablated with 248 nm excimer-laser radiation. For fluences above 200 mJ/cm², very little post-ablation debris is observed — a fact indicative of a polymer that decomposes readily into volatile, small molecular-weight compounds. Ablation-rate data have been obtained both by stylus profilometry and the quartz-crystal microbalance (QCM) technique, and the results of both methods are in good agreement. The more sensitive QCM technique first detects material removal near 20 mJ/cm², which is likely due to outgassing, surface chemistry, or low quantum-yield processes. At 37 mJ/cm², an ablation threshold with a sharp increase of the ablation rate is observed and marks the onset of efficient, explosive ablation. The densely sampled rate curve provided by the QCM permits the conclusion that an Arrhenius-like exponential does not give a satisfactory fit to the data. This demonstrates that the ablation process is not solely governed by thermal processes. Applying a Beer's-law analysis of rate versus the natural logarithm of the fluence yields excellent agreement with the data up to 300 mJ/cm². The absorption coefficent derived from this analysis agrees well (within 4%) with the value obtained from the low-intensity absorption spectrum.     

Porphyrin-sensitized laser swelling and ablation of polymer films

Laser-induced morphological changes of poly(methyl methacrylate), poly(N-vinylcarbazole), and gelatin films doped with porphyrins have been studied by etch depth measurement and scanning electron microscopy. An irreversible swelling of the irradiated surface was observed for all films in the case of low laser fluence. The swelling was replaced by ablation when the fluence was increased. The etch depth depends on the irradiation fluence and the dye concentration in the polymer. The observation of the irradiated surfaces suggests that the thermal effect is predominant both for swelling and ablation. The surface temperature at which swelling or ablation is initiated was estimated, assuming that these morphological changes take place at a certain temperature for any dye concentration in each polymer film.     

Surface ablation by excimer laser irradiation of Ti and Ti6Al4V alloy

This paper presents the surface microstructure of Ti and Ti6Al4V alloy irradiated with a high output energy XeCl ( = 308 nm) excimer laser. The treatments are carried out on both materials at two beam fluences and the effects of single- and multiple-pulse irradiation are compared. The results of the scanning electron microscopy and of the X-ray diffraction techniques suggest the possible influence of both time-behaviour and energy fluence of the laser pulse on the relative weight of the ablation rate and of the reaction product deposition rate at the sample surface.     

Direct laser ablation of sub-100 nm line structures into polyimide

Periodic line structures with a period of 167 nm and linewidths varying from 30 to 100 nm have been produced in polyimide by direct ablation with a KrF laser using an interferometric technique. The characteristics of this interferometer as it applies to the ablation of these line structures, including linewidth and alignment sensitivity, are analyzed. The ability to control the linewidth by varying the average incident fluence is described theoretically and demonstrated experimentally. This externally generated period of 167 nm also prevents the spontaneous growth of laser induced periodic surface structures (LIPSS).     

Direct generation of sub-nanosecond pulses in a high-pressure miniature excimer laser

Direct generation of subnanosecond pulses in a 9.0 cm discharge-length high-pressure XeCl laser is reported. The shortest pulse obtained was 670 ps (FWHM) with an energy of 1.2 mJ corresponding to 1.8 MW peak power.     

UV excimer laser photochemistry of hybrid organometallic compounds of gallium

The gas phase ultraviolet (UV) excimer laser induced photolysis of the gallium-alkyls Ga(t-C₄H₉) _n ^– (CH₃)_3–n (n=0, 1, 2, 3) was studied, using photolysis wavelengths of 308, 248, and 193 nm. The photofragments Ga, GaH, and GaCH₃ were detected by laser ionization time-of-flight mass spectroscopy, while the hydrocarbon products CH₄, C₂H₆, HC(CH₃)₃ and H₂C=C(CH₃)₂ were identified using Fourier transform infrared (FTIR) spectroscopy. The formation of the GaH photofragment, and a high olefin-to-alkane product ratio, for Ga(t-C₄H₉)₂(CH₃) and Ga(t-C₄H₉)₃ are interpreted to indicate a -hydrogen elimination process. However, -hydrogen elimination only occurs after fission of the weakest Ga-C bond, thus no -hydride elimination is observed for Ga(t-C₄H₉)(CH₃)₂. Detection of C₂H₆ for Ga(CH₃)₃ and Ga(t-C₄H₉)(CH₃)₂, but not for Ga(t-C₄H₉)₂(CH₃), shows that under our experimental conditions the formation of ethane is as a result of the reductive elimination of the methyl groups, and is not due to the recombination of two free methyl radicals.     

Laser-induced etching of silicon

Conventional fabrication method of porous silicon is anodisation of single crystal silicon in hydrofluoric acid. In this report, we show that it is possible to fabricate porous silicon by laser-induced etching. An earlier report by us has demonstrated the dependence of porous silicon photoluminescence characteristic on the etching laser wavelength [1]. Here we used 780 nm line from a diode laser as the etching source, and the optimum etching conditions were obtained. A simple model was proposed to explain the etching process. Scanning Electron Microscope (SEM) images of the samples support the proposed process.     

Fast degradation of fullerenes by ultraviolet laser radiation

The first observation of fullerene C₆₀ ultraviolet photolysis in hexane solution was published two years ago [1]. Similar further experiments realized with an ultraviolet lamp and solar light gave inconsistent results with ambiguous interpretations. We report the unexpectedly fast and efficient degradation of the fullerenes in n-hexane solutions, induced by an XeCl-excimer laser. Well-defined experimental conditions and good reproducibility in these experiments allow us to estimate the minimal value of the quantum yield of fullerene photolysis.     

Surface cleaning of metals by pulsed-laser irradiation in air

The surface-cleaning effect of metals was investigated using KrF-excimer-laser irradiation of metal surfaces in air. The laser-induced cleaning of copper, stainless steel and aluminum surfaces was studied. It is found that laser cleaning is an effective cleaning process for metals even if the metal surfaces are heavily contaminated. It is also found that short wavelength and pulse duration are necessary for laser surface-cleaning. The energy density of the laser pulse is an important parameter in the cleaning process. Low energy density results in a cleaner surface but a larger pulse number is required, whereas high energy density can achieve higher cleaning efficiency but the temperature rise can cause surface oxidation and secondary contamination. In contrast to the KrF-excimer-laser, the pulsed CO₂ laser is not effective in surface-cleaning. The mechanisms of laser cleaning may include laser photodecomposition, laser ablation and surface vibration due to the impact of the laser pulse. Laser cleaning provides a new dry process to clean different substrate surfaces and can replace the conventional wet cleaning processes such as ultrasonic cleaning with CFC and other organic solvents.     

Generation mechanism and thermal stability of high carrier concentrations by KrF-excimer-laser doping of Si into GaAs

The generation mechanism and thermal stability of high carrier concentrations in GaAs formed by KrF-excimer-laser doping with Si using SiH₄ gas are investigated. The channeling Particle-Induced X-ray Emission (PIXE) analysis reveals that a high substitutional fraction of over 90% and preferential replacement of Si atoms on Ga sites result in the generation of carrier concentrations as high as 5×10¹⁹ cm^–3. In addition, the thermal stability of the doped regions is studied. The high carrier concentrations in a nonthermal equilibrium state return to a thermal equilibrium state by postannealing.Presented at LASERION'93, Munich, June 21–23, 1993     

Two-wavelength operation of a tunable KrF excimer laser — A promising technique for combustion diagnostics

A KrF excimer laser was operated on two independently tunable lines. This was achieved by a double-resonator configuration with two gratings. Tuning range and gain competition were investigated. The narrow line width (<1 cm^–1) and the independent tunability make this laser ideal for simultaneous spectroscopic detection of two species and temperature measurements in combustion processes.     

Threshold behavior in polyimide photoablation: Single-shot rate measurements and surface-temperature modeling

The ablation rate of Kapton-type polyimide has been measured as a function of incident fluence and excimer laser wavelength using a sensitive quartz-crystal microbalance (QCM). The experiments were performed such that the fluence and the ablated depth were known for each laser pulse, avoiding the need to average rate and fluence data over many pulses. By limiting the investigations to the low-fluence regimes near ablation threshold, high precision and detailed curve shapes were obtained. It was found that the ablation rate increases smoothly and exponentially with increasing fluence for 248, 308, and 351 nm wavelengths. This exponential behavior was modeled using an Arrheniustype thermal rate equation. In contrast, the 193 nm curve is linear in fluence, displays a sharp threshold, and is consistent with a possible photochemical ablation mechanism. Using a sophisticated surface temperature modeling code, the maximum laser induced surface temperature at the fluence at which ablation can first be detected is found to be the same, 850° C, for all four wavelengths. This ablation temperature is significantly higher than the approximately 500° C temperature at which Kapton starts to degrade under isothermal heating conditions.     

Depth profiling of copper thin films by resonant laser ablation

In Resonant Laser Ablation (RLA), material is related and selectively ionized by a low-energy pulse from a tunable laser. The selectivity and efficiency allow detection and quantitation at very low concentrations. We demonstrate that RLA has potential use in profiling thin layer and multilayer structures. Quantitative results are reported on the analysis of 20 and 100 Å copper thin films on Si(110) surfaces. Removal rates range from 10^–3 to 10^–2 Å/shot. Prospects for interrogation of dopants and impurities are also evaluated.     

Ablation of poly(methyl methacrylate) and poly(2-hydroxyethyl methacrylate) by 308, 222 and 193 nm excimer-laser radiation

Data on the ablation of Poly(Methyl MetAcylate) (PMMA) and Poly(2-Hydroxyethyl MetAcylate) (PHEMA) with 0%, 1% and 20% of Ethylene Glycol DiMethAcrylate (EGDMA) as crosslinking monomer by 193, 222 and 308 nm laser radiation are presented. Direct photoetching of PMMA at 308 nm is demonstrated for laser fluences ranging from 2 to 18 J/cm². The ablation rate of PHEMA is lower than the corresponding to PMMA and decreases when the amount of EGDMA increases. The determination of the absorbed energy density required to initiate significant ablation suggests that the photoetching mechanism is similar for all the polymers studied and is a function of the irradiation wavelength. The Beer-Lambert law, the Srinivasan, Smrtic and Babu (SSB) theory and the kinetic model of the moving interface are used to analyze the experimental results. It is shown that only the moving interface theory fits well the etch rate for all the selected polymers at the three radiation wavelengths.     

Peculiarities of KrF excimer vibrational relaxation in low-pressure Kr/F2 mixtures excited by a short pulse

The importance of excimer vibrational relaxation is manifested once again by the example of the low-pressure Kr/F₂ gain medium excited by a short pulse. The pressure is determined at which a sharp fall of the population efficiency of low KrF(B) vibrational levels should appear. Time peculiarities of the gain are investigated analytically for short-pulse excitation operation.     

VUV spectra from the krypton-fluoride ionic excimer

New continuous VUV radiation near 148 nm was observed from Kr/NF₃/He and Kr/F₂/He mixtures under X-ray excitation from a laser-produced plasma. Theoretical and experimental analysis shows that the continuum can be attributed to the transition of the ionic excimer Kr²⁺F^–.     

Acoustic wave monitoring of the excimer laser ablation of YBCO high-Tc superconductor

Monitoring the amplitude and the delay of arrival of the pressure waves generated during the interaction of laser pulses with YBCO in air, we can determine the vaporization and the ablation thresholds, the etching rate, the change of the acoustic wave velocity and the effect of plasma shielding on the etching rate. The steep increase of the amplitude and the order-of-magnitude increase of the etching rate above the ablation threshold, suggest that the laser–target coupling mechanism changes from (thermal) vaporization below threshold to a rapid solid-to-gas phase transition. The dumping of the acoustic waves following the ablation with successive laser pulses correlates with the evolution of the YBCO high-T_c superconductor surface morphology, which is known to relate to the deposition rate and the surface morphology of pulsed-laser-deposited high-T_c thin films. Received: 7 January 2000 / Accepted: 9 October 2000 / Published online: 25 July 2001