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.     

Surface foaming of collagen, chitosan and other biopolymer films by KrF excimer laser ablation in the photomechanical regime

Collagen, an important material made of a protein of the extracellular matrix, was extracted from rat tail tendons by acetic acid dissolution, and dry glassy films (15% water content) with smooth surfaces were casted from the solution with a thickness of ∼25 μm. Collagen and similar biopolymer films surface were exposed to single pulses of radiation of the KrF laser with increasing fluence. A white damaged area appears on the treated surface at a threshold of 0.5 J/cm² with a single pulse and becomes more visible for higher fluence. SEM and profilometry of the ablated surface displays an important swelling (∼5–7 μm) and a microscopic foam structure indicative of the laser induced expansion of the excited material. This process is due to the explosive ablation (a critical phenomenon also called explosive boiling or phase explosion) of the irradiated material and produces upon laser heating a high concentration of bubbles within the polymer because of the relatively large absorption depth (20 μm) and the presence of a large amount of water in the material. Further bubble colliding and bursting produces a three-dimensional polymer micro-foam with interconnected pores. This is the first this result has been reported. The laser induced micro-foam may display some interesting properties for new applications. PACS 42.62; 61.82; 42.70-aThis revised version was published online in June 2005 with corrections to equations 7, 9 and 10.     

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.     

Efficient micromachining of poly(vinylidene fluoride) using a laser-plasma EUV source

In this paper an efficient micromachining of poly(vinylidene fluoride) (PVDF) by direct photo-etching with a laser-plasma EUV (extreme ultraviolet) source was demonstrated for the first time. Mass spectroscopy was employed to investigate the ablation products and revealed emission of numerous molecular species of C-containing fragments of the polymer chain. Chemical surface changes after irradiation were investigated using X-ray photoelectron spectroscopy (XPS). The XPS spectra obtained for PVDF samples, irradiated with low and high EUV fluence, indicate significant differences between chemical structures in near-surface layers. It was shown that irradiation with low fluence results in defluorination and thus carbon enrichment of the polymer in near-surface layer. In contrary, irradiation with high fluence leads to intense material ablation and hardly modifies the chemical structure of the remaining material.     

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     

Mechanism of backside etching of transparent materials with nanosecond UV-lasers

In consequence of high interest in micro- and nanomachining of transparent materials by laser irradiation, studies on the mechanism of laser-induced backside wet etching (LIBWE) are presented. To reveal the role of the surface modification due to LIBWE the backside ablation (BSA) of LIBWE-modified fused silica (mFS) surfaces at 248 nm was investigated. The threshold fluence and the etch rate of BSA are similar to that of LIBWE and amount ∼250 mJ/cm² and 30 nm for 1 J/cm², respectively. The sample transmission after backside ablation of mFS increases and proves the decreasing thickness of the absorbing layer. Time-resolved reflection studies at LIBWE and BSA of mFS show similar patterns in the backside reflection that can be assigned an ablation process as the comparison to thin polymer films demonstrates. By fitting the BSA data to an exponential decay absorption model a modification depth and a surface absorption of about 38 nm and α ^S ∼1.3×10⁷ m⁻¹ were calculated, respectively. In conclusion of the results a new model for LIBWE is proposed.     

Laser-induced high-quality etching of fused silica using a novel aqueous medium

Laser-induced backside wet etching of fused-silica plates using an aqueous solution of naphthalene-1,3,6-trisulfonic acid trisodium salt (Np(SO₃Na)₃) is reported. A KrF excimer laser was employed as a light source. The etch rate varied greatly with the concentration of the solution and the laser fluence. For lower concentration solutions, the etch rate increased linearly with laser fluence. For highly concentrated solutions, however, the etch rate increased abruptly at higher fluence. Well-defined line-and-space and grid micropatterns were fabricated using a low etch rate. The etched surface was as flat as the surface of the virgin plates and the etched pattern was free of debris and microcracks. The formation and propagation of shockwaves and bubbles in the solution during the etch process were monitored. High pressure, as well as the high temperature generated by the photothermal process, plays a key role in the etching process. Received: 8 April 2002 / Accepted: 12 April 2002 / Published online: 19 July 2002     

Effect of irradiation history on the preparation of laser induced periodic microstructure on polyimide surface

Although UV laser is proved to be an effective tool to prepare microstructure on polymer surface, laser ablation accompanied by the formation of laser induced periodic surface structure (LIPSS) limits its application in many fields. The purpose of this report is to investigate the effect of pre-irradiation in advance, using a low-fluence laser, on the LIPSS formation. The properties of pre-irradiated PI films were characterized by X-ray photoelectron spectroscopy (XPS), surface tension based on the contact angle measurements and UV-vis spectra. It was found that pre-irradiation at low fluence led to the changes in surface property such as chemical components though no LIPSS was formed. As a result, threshold of LIPSS formation on such pre-irradiated PI film decreased and fine LIPSS with deeper amplitude was obtained.     

Polymer self-assembled nano-structures and surface relief gratings induced with laser at 157 nm

Surface relief gratings (SRG) and self-organized nano-structures induced by laser light at 157 nm on the fluoropolymer poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA), films were obtained under well-controlled light exposure conditions. Regular and semi-regular spaced self-organized grating-like structures were created on polymeric films for ∼7.5-100 mJ/cm² laser energy fluence. For lower laser fluence, the surface morphology of light exposed/non-exposed areas exhibited irregular-like structure morphologies, while polymer surface irradiation with energy fluence higher than 150 mJ/cm² causes progressively fading out of the regular patterns. Under the specific experimental conditions, the SRG and self-organization patterning have their origin in the development of a surface thermal instability (Rayleigh's instability), which is resolved itself into regular patterns on the surface of the fluoropolymer film. The thermal instability is due to the explosive polymer surface photo-dissociation at 157 nm and the build up of longitudinal and periodic surface stress, which eventually create the SRG and the self-assembled structures on the polymer.     

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.     

Dopant-induced excimer laser ablation of poly(tetrafluoroethylene)

Clean ablation of poly(tetrafluoroethylene) (PTFE) at etch rates in excess of 7µm/pulse has been achieved with an excimer laser using 308nm radiation and a 25 ns pulse width. This was accomplished by doping the ultraviolet-transparent PTFE polymer with polyimide. Ablation rates were investigated as a function of fluence in the range from 1 to 12J/cm² and dopant levels up to 15% (wt/wt). Results show that at a given fluence there exists an optimum absorption coefficient _max, for which maximum ablation rates are achieved. The value of _max was found to decrease with increasing fluence. The relationship between _max and fluence was determined from existing ablation rate models and found to compare favorably with empirical results.     

Effect of laser-ablated copper nanoparticles on polymerization of 1,1,3,3-tetraphenyl-1,3-disilacyclobutane

We have studied the effect of copper nanoparticles produced by laser ablation on the ring-opening polymerization of 1,1,3,3-tetraphenyl-1,3-disilacyclobutane (TPDC). The particle size and distribution of laser-ablated, copper nanoparticles were controlled by laser-ablation conditions such as ambient pressure, laser fluence, and distance between target and substrate. Laser-ablated, copper nanoparticles induced polymerization of TPDC effectively, resulting in formation of poly(diphenylsilylenemethylene) (PDPhSM) thin films. The polymerization efficiency depended mainly on the particle size and the surface concentration of copper nanoparticles deposited on the TPDC films by laser ablation. No clear tendency was observed between oxidation of Cu nanoparticles and polymerization efficiency. This technique enables us to easily fabricate PDPhSM thin films and may become a new method for fabricating polymer–metal nanocomposites. PACS 81.05.Lg; 82.35.Np; 82.50.Hp     

Enhancement of pulsed laser ablation assisted with continuous wave laser irradiation

Continuous wave(CW) laser irradiation is employed to enhance the pulsed laser ablation of silicon and stainless steel(316 L)samples. Different surface temperatures generated by the CW laser irradiation are set as the initial working circumstance for the pulsed laser ablation. The diameter and depth of laser-ablated craters are measured to study threshold fluence, pulse incubation coefficient and ablation rate under different surface temperatures. Numerical simulation employing Heat Transfer in Solid and Deformed Geometry Interface modules in COMSOL is performed to estimate ablation rate theoretically based on Hertz-Knudsen equation. The realized crater-related data are analyzed to further obtain their dependences on surface temperature. The parametric and morphological studies indicate that the weakened plasma shielding effect and thermal diffusion in the ablated region induced by the CW laser irradiation lead to the enhanced pulsed laser ablation significantly.     

Dynamics of excimer laser ablation of polyimide determined by time-resolved reflectivity

The time-dependent intensity profile of pulsed KrF excimer laser radiation reflected from polyimide is determined over a range of laser fluences, from well below to above the ablation threshold. The reflected laser beam is truncated once the incident laser radiation exceeds a threshold fluence, i.e., truncation depends on the energy per unit area and not on the intensity, analogous to results for the ablation threshold and the etch depth per pulse. The threshold fluence for pulse truncation corresponds to the onset of ablation. The results indicate that the truncation is not due to laser plasma interactions at these fluences. A general mechanism is discussed involving a time dependent index of refraction.     

Hardening of smooth pulsed laser deposited PMMA films by heating

Smooth poly(methyl methacrylate) (PMMA) films without any droplets were pulsed laser deposited at a wavelength of 248 nm and a laser fluence of 125 mJ/cm². After deposition at room temperature, the films possess low universal hardness of only 3 N/mm². Thermal treatments up to 200°C, either during deposition or afterwards, lead to film hardening up to values of 200 N/mm². Using a combination of complementary methods, two main mechanisms could be made responsible for this temperature induced hardening effect well above the glass transition temperature of 102°C. The first process is induced by the evaporation of chain fragments and low molecular mass material, which are present in the film due to the ablation process, leading to an increase of the average molecular mass and thus to hardening. The second mechanism can be seen in partial cross-linking of the polymer film as soon as chain scission occurs at higher temperatures and the mobility and reactivity of the polymer material is high enough.     

Growth and characterization of silicon nitride films on various underlying materials

Characteristics of silicon nitride (SiN_x:H) films, grown by plasma enhanced chemical vapor deposition (PECVD) on various metals such as Ta, IrMn, NiFe, Cu, and CoFe at various temperatures down to 100 °C, were studied using measurements of BHF etch rate, surface roughness and Auger electron spectroscopy (AES). The results were compared with those obtained for SiN_x:H films on Si. The deposition rate of SiN_x:H films increased slightly as deposition temperature decreased, and showed a weak dependence on the underlying materials. The surface of the nitride films deposited on all underlying materials at lower temperatures (below 150 °C) became rougher. In particular, a bubble-like surface was observed on the nitride film deposited on NiFe at 100 °C. At higher deposition temperatures (above 200 °C), SiN_x:H films on all the above metals had small RMS values, except for films on Cu which cracked at 250 °C. BHF (10:1) etch rate increased dramatically for nitride films deposited below 150 °C. For different underlying films, the BHF etch rate was quite different, but exhibited the same trend with decrease in deposition temperature. AES measurements showed that Si and N concentrations in the SiN_x:H films were only slightly different for the various deposition temperatures and underlying materials. AES depth profile of nitride films indicated that both surface O content and the depth of oxygen penetrating into SiN_x:H increased for low temperature-deposited films. However, there was no observed oxygen signal from within the films, even for films deposited at 100 °C, and both Si and N concentrations were uniform throughout the film. Received: 26 October 2001 / Accepted: 2 March 2001 / Published online: 20 June 2001     

Laser ablation of polysulfone films: a laser ionization TOF mass spectrometric study

2 . Major peaks were assigned to direct fragments and recombination products ejected from the PS surface. The arrival profiles of these ablation products varied from product to product and were fitted by using a shifted Maxwell–Boltzmann distribution with a center-of-mass flight velocity [(1.4-5.6) ×10⁵ cm/s] and a Knudsen layer temperature (350–3810 K). Two types of ablation products, whose velocities and temperatures showed different dependences on laser fluence, were found to exist. Dynamical aspects in the decomposition of the polymer chain, the ejection of various fragments, and their expansion are discussed on the basis of a photothermal ablation model, where a heated surface layer with a temperature gradient along its depth plays an important role. Received: 11 August 1998/Accepted: 12 August 1998     

Temperature dependence of the luminescence lifetime of a europium complex immobilized in different polymer matrices

The temperature dependence of the luminescence lifetime of temperature sensor films based on europium (III) thenoyltrifluoroacetonate (EuTTA) as sensor dye in various polymer matrices such as polystyrene (PS), polymethylmethacrylate (PMMA), polyurethane (PU) and model airplane dope was studied and compared. The luminescence lifetime of EuTTA was found to depend on the polymer matrix. The temperature sensitivity of lifetime was maximum for EuTTA-PS coating in the temperature range of 10-60 °C. The effect of concentration of the sensor dye in the polymer on the lifetime and temperature sensitivity was also studied.     

In situ ellipsometry study of atomic hydrogen etching of extreme ultraviolet induced carbon layers

Atomic hydrogen based etching is generally considered an efficient method for the removal of carbon films resulting from photo-induced hydrocarbon dissociation, as occurs in extreme ultraviolet (EUV) photolithography environments. The etch rate of atomic hydrogen for three different kinds of carbon films was determined, namely for EUV-induced carbon, hot filament evaporated carbon and e-beam evaporated carbon. The etching process was monitored in situ by spectroscopic ellipsometry. The etch rate was found to depend on the type of carbon (polymer or graphite-like), on the layer thickness, and on the temperature. The EUV-induced carbon shows the highest etch rate, with a value of ∼0.2 nm/min at a sample temperature of 60 °C. The more graphite-like carbon layers showed an etch rate that was about 10 times lower at this temperature. An activation energy of 0.45 eV was found for etching of the EUV-induced carbon layer.