Fundamentals and applications of polymers designed for laser ablation

The ablation characteristics of various polymers were studied at low and high fluences for an irradiation wavelength of 308 nm. The polymers can be divided into three groups, i.e. polymers containing triazene groups, designed ester groups, and reference polymers, such as polyimide. The polymers containing the photochemically most active group (triazene) exhibit the lowest thresholds of ablation (as low as 25 mJ cm^-2) and the highest etch rates (e.g. 250 nm/pulse at 100 mJ cm^-2), followed by the designed polyesters and then polyimide. Neither the linear nor the effective absorption coefficients have a clear influence on the ablation characteristics. The different behavior of polyimide might be explained by a pronounced thermal part in the ablation mechanism. The laser-induced decomposition of the designed polymers was studied by nanosecond interferometry and shadowgraphy. The etching of the triazene polymer starts and ends with the laser pulse, indicating photochemical ablation. Shadowgraphy reveals mainly gaseous products and a pronounced shockwave in air. The designed polymers were tested for an application as the polymer fuel in laser plasma thrusters. Received: 21 October 2002 / Accepted: 20 January 2003 / Published online: 28 May 2003 RID="*" ID="*"Corresponding author. Fax: +41-56/3104-412, E-mail: thomas.lippert@psi.ch     

Polymer ablation: From fundamentals of polymer design to laser plasma thruster

UV-Laser ablation of polymers is a well-established method to structure and deposit polymers, but the mechanisms of ablation are still controversial, i.e. photothermal or photochemical processes. An approach to probe the ablation mechanisms and to improve ablation is to incorporate photoactive groups into the polymer structure.The investigation of the ablation behavior of designed triazene polymers showed that the ablation mechanism is always a combination of both photothermal and photochemical processes, but the ratio can be changed by using different polymers and irradiation wavelengths. Also the quality of structures in the triazene polymers is superior at an irradiation wavelength of 308 nm compared to commercially available polymers.Polymers can be designed not only for UV irradiation, but also for applications in the IR range, but with different requirements. One application for designed polymers in the near-IR range is as fuel for the laser plasma thruster, which is used as propulsion system for small satellites. With commercially available polymers the necessary thrust could not be achieved. A specially designed polymer-absorber system for this application produce more energy in the form of thrust, than the laser delivered.     

Nanosecond surface interferometry measurements on designed and commercial polymers

The effect of the ablation mechanism on surface morphology changes during an ablation process was studied by comparing three different polymers: a triazene polymer, a polyimide and poly(methylmethacrylate) (PMMA) with nanosecond surface interferometry. The triazene polymer, for which only indications for a photochemical ablation mechanism had been detected in previous studies, revealed no surface swelling, which could be attributed to a thermal ablation mechanism. For polyimide, a photothermal ablation mechanism is usually used to describe the ablation process at irradiation wavelengths 248 nm. However, the interferometric measurements do not show any surface swelling, which would be a clear indication for a thermal ablation mechanism. A surface swelling was only detected for PMMA with irradiation at 248 nm and fluences below the threshold of permanent surface modification. The detected phase shift, which is proportional to the change of the film thickness and the refractive index, can be explained by the opposite signs of the thermal expansion coefficient and the thermal refractive-index coefficient. PACS 52.38.Mf; 42.87.Bg; 71.20.Rv     

Characterisation of combined positive-negative photoresists by excimer laser ablation

Novel photopolymers containing side groups based on o-methoxycinnamylidenemalonic acid, which undergo selective photo-crosslinking without destruction of the polymer backbone upon irradiation at 5>395 nm, have been developed for potential applications as combined positive-negative resists and multilayer resists. An XeCl excimer laser (5=308 nm, F=20 ns) was used as the irradiation source to study the ablation and microstructuring characteristics of the polymers. The materials were structured before and after crosslinking. The ablation rate was analysed by varying the fluence (0.01-10 J/cm²) and the number of pulses for a given irradiation area. Etch rates of about 2 7m per pulse at a fluence of 9 J/cm² could be achieved for all polymers. The polymer with triazene groups reveals a higher etch rate at low fluences (less than 300 mJ/cm²) than the polymer without a triazene group. The experimentally observed threshold fluence for the triazene-containing polymer is about 30 mJ/cm². Using a Schwarzschild-type reflection objective (152), microstructures with a resolution in the micron range were produced on both polymer films. The quality of the structures was evaluated by scanning electron microscopy. The results indicate that the new polymers could be used as resists for excimer laser ablation lithography.     

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.     

Tritium recovery from co-deposited layers using 193-nm laser

Recovery of tritium from co-deposited layers formed in deuterium–tritium plasma operations of the TFTR (Tokamak Fusion Test Reactor) was investigated by the use of an ArF excimer laser operating at the wavelength of 193 nm. At the laser energy density of 0.1 J/cm², a transient spike of the tritium-release rate was observed at initial irradiation. Hydrogen isotopes were released in the form of hydrogen-isotope molecules during the laser irradiation in vacuum, suggesting that tritium can be recovered readily from the released gases. In a second experiment, hydrogen (tritium) recovery from the co-deposited layers on JT-60 tiles that had experienced hydrogen-plasma operations was investigated by laser ablation with a focused beam of the excimer laser. The removal rate of the co-deposited layers was quite low when the laser energy density was smaller than the ablation threshold (1.0 J/cm²), but reached 1.1 μm/pulse at the laser energy density of 7.6 J/cm². The effective absorption coefficient in the co-deposited layers at the laser wavelength was determined to be 1.9 μm^-1. The temperature of the surface during the irradiation at the laser energy density of 0.5 J/cm² was measured on the basis of Planck’s law of radiation, and the maximum temperature during the irradiation decreased from 3570 K at the initial irradiation to 2550 K at the 1000th pulse of the irradiation. Received: 5 August 2002 / Accepted: 7 August 2002 / Published online: 28 October 2002 RID="*" ID="*"Corresponding author. Fax: +81-29/2825917, E-mail: shu@tpl.tokai.jaeri.go.jp     

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.     

Experimental studies and thermal modelling of 1064- and 532-nm Nd:YVO4 micro-laser ablation of polyimide

Experiments and thermal modelling of polyimide ablation using the fundamental 1064-nm emission from a 20-kHz nanosecond diode-pumped solid-state Nd:YVO₄ micro-laser are described and compared with findings for the 532-nm doubled output. For exposures restricted to short pulse trains, it is found that micron-scale-size ablation features can be defined with this laser, even though polyimide films have weak absorption at 1064 nm and relatively weak absorption at 532 nm. There is evidence at both wavelengths of an incubation effect, driven by thermal modification of the polymer and, with long-term exposure at 1064 nm, Raman micro-spectroscopy reveals a progressive growth of predominantly amorphous carbon in the ablation site. Calculations of the temperature rise produced in the polymer by exposure to a high-repetition-rate pulse train are described that aid an understanding of the thermal aspects of the interaction at the two wavelengths. PACS 42.55.Xi; 44.10.+i; 52.38.Mf     

Characterization of laser-ablated and chemically reduced silver colloids in aqueous solution by UV/VIS spectroscopy and STM/SEM microscopy

Silver colloids in aqueous solution were studied by different scanning microscopy techniques and UV/VIS spectroscopy. The silver colloids were produced either by chemical reduction or by nanosecond laser ablation from a solid silver foil in water. Variation of laser power and ablation time leads to solutions of metal clusters of different sizes in water. We characterized the electronic absorption of the clusters by UV/VIS spectroscopy. STM (scanning tunneling microscope) imaging of the metal colloids shows atomic resolution of rod- or tenon-like silver clusters up to 10-nm length formed by laser ablation. Our scanning electron microscope measurements, however, show that much larger silver colloids up to 5-μm length are also formed, which are not visible in the STM due to their roughness. We correlate them with the long-wavelength tail of the multimodal UV/VIS spectrum. The silver colloids obtained by chemical reduction are generally larger and their electronic spectra are red-shifted compared to the laser-ablated clusters. Irradiation of the colloid solution with nanosecond laser pulses of appropriate fluence at 532 nm and 355 nm initially reduced the colloid size. Longer irradiation at 355 nm, however, leads to the formation of larger colloids again. There seems to be a critical lower particle size, where silver clusters in aqueous solution become unstable and start to coagulate. Received: 24 June 2002 / Revised version: 25 July 2002 / Published online: 25 October 2002 RID="*" ID="*"This work is part of the thesis of H. M?ltgen RID="**" ID="**"Corresponding author. Fax: +49-211/811-5195, E-mail: kleinermanns@uni-duesseldorf.de     

Photocontrolled mechanical phenomena in photochromic doped polymeric systems

This work examines volume changes at the sub-micron scale, induced photochemically in polymeric matrices doped with photochromic molecules. To achieve this, spiropyran is employed as a photochromic molecule embedded in polyethylmethacrylate-co-methylacrylate (PEMMA) matrices. Spiropyran can be reversibly interconverted to merocyanine, its coloured isomer, by irradiation at 248 nm and 532 nm, correspondingly. It is demonstrated that the interconversion between the two forms activates volume changes in the polymer matrix. To this end, off-axis reflection holographic interferometry is employed as a sensitive probe of the induced volume changes. This scheme provides a novel method for controlling sub-micron volume changes reversibly, as required in several microactuator designs. Received: 17 April 2002 / Accepted: 18 April 2002 / Published online: 10 September 2002 RID="*" ID="*"Corresponding author. Fax: +30-810/391-318, E-mail: nassia@iesl.forth.gr     

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.     

Hybrid laser processing for microfabrication of glass

Hybrid laser processing for the precision microfabrication of glass materials, in which the interaction of a conventional pulsed laser beam and a medium on the material surface leads to effective ablation and modification, is reviewed. A major role of the medium is to produce strong absorption of the conventional laser beam by the material. Simultaneous irradiation by a vacuum ultraviolet (VUV) laser beam that possesses an extremely small laser fluence and an ultraviolet (UV) laser greatly improves the ablation quality and modification efficiency for fused silica (VUV-UV multiwavelength excitation process). The metal plasma generated by the laser beam effectively assists high-quality ablation of transparent materials by the same laser beam, resulting in microstructuring, cutting, color marking, printing, and selective metallization of glass materials (laser-induced plasma-assisted ablation (LIPAA)). The detailed discussion presented here includes the ablation mechanism of hybrid laser processing. Received: 18 December 2002 / Accepted: 20 January 2003 / Published online: 28 May 2003 RID="*" ID="*"Corresponding author. Fax: +81-48/462-4682, E-mail: ksugioka@postman.riken.go.jp     

Laser-induced nano-patterning by means of interference subpatterns generated by microspheres

Interference patterns generated by a regular lattice of SiO₂ microspheres on a transparent support are used for the surface patterning of polyimide (PI) foils. Using 248 nm excimer-laser radiation, thousands to millions of holes with a full width at half maximum (FWHM) of 160±40 nm can be generated with a single laser pulse. Received: 1 March 2002 / Accepted: 4 March 2002 / Published online: 10 September 2002 RID="*" ID="*"Corresponding author. Fax: +43-732/2468-9242, E-mail: dieter.baeuerle@jku.at     

Detection of neutral products formed during excimer laser ablation of polyimide by UV and VUV laser photoionization/mass spectrometry

Some of the neutral species which are produced in the laser ablation of polyimide have been characterized using multiphoton ionization/time of flight mass spectrometry. Three different wavelengths (193 nm, 157 nm, and 118 nm) have been used in an attempt to effect soft ionization of the products formed during or after the initial laser ablation of the polymer. Neutral photo-ablation products detected using this scheme range from atomic to high molecular weight species which, depending on the probe wavelength, include pure carbon clusters as well as a broad distribution of heteroatom containing clusters. However, there is virtually no overlap in the mass spectra recorded at each probe wavelength. When probing with 193 nm, marked changes are observed in the mass spectra as a function of the probe flux used. At moderate fluxes, pure carbon clusters (fullerenes) are observed. The identification of a large distribution of species other than pure carbon clusters is in dramatic contrast to the recent observation [W.R. Creasy, J.T. Brenna: Chem. Phys. 126, 453 (1988)] of the positively charged ionic species produced, which are solely carbon clusters. These results suggest that the neutral and ionic products observed after ablation of the polymer are due to both condensation of the atomic and molecular fragments which form during the ablation laser pulse and nascent polymer fragments. Various implications of this result for the unambiguous determination of the true ablation product distribution are discussed.     

Changes in the etch rate of photosensitive polymers as a function of the pulse number

The ablation rates of a polyimide and a triazene polymer were studied gravimetrically by a quartz micro balance for 248-nm and 308-nm irradiation. Special care was taken to examine the dependence of the ablation rate at constant fluences for single pulses and the influence of consecutive pulses at the same position. A clear trend was observed in these measurements, i.e., that the mass loss after the first pulse is always different from values for the following pulses. This implies that it is very difficult to determine true ablation rates, which are the foundation of most ablation models. The differences of the mass loss between the first pulse and the following pulses is most probably due to carbonization of the material, resulting in varying ablation rates for the following pulses. The ablation rates are thus not a real material property but a superposition of the material ablation rates with the ablation rates of carbon and carbonized material. PACS 52.38.Mf; 71.20.Rv; 07.10.Lw     

Temperature and excitation wavelength dependencies of 3-pentanone absorption and fluorescence for PLIF applications

The temperature and excitation wavelength dependencies of 3-pentanone absorption and fluorescence were studied in support of planar laser-induced fluorescence (PLIF) imaging of temperature and mixture fraction in flows of practical interest. The temperature dependencies (300–875 K) of absorption and fluorescence were measured for gaseous 3-pentanoneat atmospheric pressure in a nitrogen bath gas using 248, 266, and 308 nm excitation. The results indicate that the fluorescence signal per unit mole fraction using 248 nm excitation is highly temperature-sensitive below 600 K, while the signal from 308 nm excitation is not temperature sensitive below 500 K. For quantitative measurements over a broad range of temperatures, one must choose excitation schemes carefully to balance the trade-off between measurement sensitivity and the amount of signal at the expected conditions. As an example of such a choice and to show the capabilities of ketone PLIF techniques, we include temperature and mixture fraction images of a 300–650 K heated air jet using near-simultaneous 308 and 266 nm excitation. Received: 29 May 2002 / Revised version: 5 November 2002 / Published online: 26 February 2003 RID="*" ID="*"Corresponding author. Fax: +1-650/723-1748, E-mail: jkoch@stanford.edu RID="**" ID="**"E-mail: hanson@me.stanford.edu     

Imaging-XPS/Raman investigation on the carbonization of polyimide after irradiation at 308 nm

The laser ablation of polyimide was studied using 308 nm laser irradiation 𙜡 mJ cm^-2. Confocal Raman microscopy revealed the deposition of carbon surrounding the ablation crater, which consists of amorphous carbon with some crystalline features. Inside the crater, graphitic material was detected on top of the cones, very similar to the material from cw-Ar⁺ ion laser irradiation. FT-Raman measurements reveal the presence of intermediates of the polyimide decomposition. Imaging-X-ray photoelectron spectroscopy confirmed the deposition of carbon material surrounding the ablation crater and showed that the oxygen and nitrogen contents of the remaining material decrease.     

Comparison of the transmission behavior of a triazeno-polymer with a theoretical model

The threshold fluence,F _Th, of ablation of a triazeno-polymer was measured in the low fluence range for thin films using conventional UV-spectroscopy. It was found that there is a clearly definedF _Th for 308 nm irradiation between 20 and 25 mJ cm^–2. In the case of 248 nm irradiation, a threshold fluence range between 16 and 32 MJ cm^–2 was found. The ablation rate for both irradiation wavelengths depends on film-thickness. For the XeCl excimer-laser, the point at which the rate becomes independent of thickness was observed to lie at a value which did not correspond to the calculated laser penetration depth, whereas for the KrF laser the independence was not reached within the applied thickness range (up to 0.35 m). Additional transmission measurements have been performed showing that the target transmission at 248 nm increases only slightly, whereas for 308 nm the transmission increases by a factor of approximately 4. This result shows that dynamic target absorption properties are very important for describing the ablation process. The results derived from the transmission studies and etch rates were analyzed theoretically with a two-level model of chromophore absorption. For 248 nm irradiation this model can describe the transmission behavior and the ablation rate. In the case of 308 nm irradiation, it was only possible to match one data set. A good agreement with the experimental transmission ratio does not match the ablation rate and vice versa.