Ultraviolet-laser-induced permanent electrical conductivity in polyimide

When polyimide (Kapton) is irradiated by a krypton fluoride (KrF) laser, an increase of the electrical conductivity of up to 16 orders of magnitude is observed. In the high conduction regime, the resistivity is about 0.1 cm, the current voltage characteristic is ohmic and the contacts of gold and silver with the irradiated conducting polymer are also ohmic. The conduction mechanism is phonon-assisted variable range hopping, evident from the observed temperature and electric field dependence of the resistivity at low conductivities. The laser-induced conductivity depends on the ambient atmosphere during irradiation. Transmission spectroscopy in the visible region and infrared Fourier transform spectroscopy have been used to characterize the material. A thermal mechanism is proposed for the formation of conducting polyimide, by excimer-laser irradiation.     

Thermal and mechanical coupling between successive pulses in KrF-excimer-laser ablation of polyimide

Multiple-shot effects in laser processing and ablation of polyimide are examined and are found to be the dominant phenomena for processes involving several hundreds or thousands of pulses. For fluences less than 260 mJ/cm², it was found that it is impossible to cut through 75 m polyimide foils for an arbitrarily large number of excimer pulses even though this fluence is more than ten times the single-shot ablation threshold. The halt in etching is due to the formation, over a number of shots, of a robust carbon matrix with a deep surface roughness which is also responsible for laser-induced electrical conductivity. The effect of thermal coupling between successive shots is shown to be a dominant factor in determining the electrical properties of the carbon layer. Differences in electrical conductivity of up to 12 orders of magnitude were found for only small differences in repetition rate. Transmission electron microscopy revealed the changes in microstructure responsible for the dramatic differences in electrical properties.     

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.     

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).     

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.     

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.     

Plume temperature in the laser ablation of polyimide films measured by infrared emission spectroscopy

The infrared emission spectrum of the plume produced by KrF excimer laser ablation of polyimide films in air and in He was measured in the 680 to 1580 cm^–1 wavenumber range. Using 400 mJ/cm² laser pulses of 248 nm and 35 ns duration yielded a strong emission band characteristic of thev ₂ transitions of hot HCN molecules. Band counters calculations were carried out of thev ₂ emission expected from HCN in thermal equilibrium at various temperatures. They indicate that except for a slight deviation of the measured data from thermal equilibrium, the best fit of the observed results is obtained at a plume temperature of 2250±150K.     

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.     

Structure reorganization in polymer films of nafion due to swelling studied by scanning force microscopy

The surface morphology of dry and swollen Nafion films was investigated on the micrometer and nanometer scale by scanning force microscopy. The results show that the disordered network structure of dry films undergoes a reorganization process in the course of swelling and transforms into an ordered structure of parallel fibrils. No substantial changes in the fibril dimensions were found in the swollen state. This can be an indicator that swelling occurs at the supramolecular level.     

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     

Interfacial microstructure and reaction at the spin-coated fluorinated polyimide/Al interface: surface-enhanced X-ray diffraction and TEM studies

2 multilayers by means of X-ray diffraction, transmission electron microscopy, and an ellipsometer. The FPI precursor, a solution of PMDA/6FDA/TFMOB/PPD was spin-coated onto the Al layer and then cured at 400 °C for one hour. It is found that the moisture and oxygen from the FPI layer released during thermal treatment can lead to the oxidation of the interface between the Al and the FPI. The TEM cross-sectional images and the electron diffraction patterns indicate that the oxidized interface is amorphous. The oxidation product is identified to be Al₂O₃. The oxidation onset temperature is determined to be 415 °C, which is slightly higher than the curing temperature. The oxidation of the FPI/Al interface results in an increase in the electrical resistance of the Al layer, and thus may lead to a reduction in its effective electrical thickness. Received: 21 May 1997/Accepted: 27 May 1997     

Model for laser-induced thermal degradation and ablation of polymers

Ablation of organic polymers is described on the basis of photothermal bond breaking within the bulk material. Here, we assume a first-order chemical reaction, which can be described by an Arrhenius law. Ablation starts when the density of broken bonds at the surface reaches a certain critical value. In order to understand the ablation behavior near the threshold fluence, φ_th, non-stationary regimes must be considered. The present treatment reveals several qualitative differences with respect to models that treat ablation as a surface process: (i) Ablation starts sharply with a front velocity that has its maximum value just after the onset. (ii) The transition to the quasi-stationary ablation regime is faster. (iii) Near threshold, the ablated depth h has a square-root dependence on laser fluence, i.e., h∝(φ-φ_th)^1/2. The ablation velocity is very high even near φ_th. (iv) With φ≈φ_th ablation starts well after the laser pulse. (v) The depletion of species is responsible for the Arrhenius tail observed with fluences φ≤φ_th. (vi) Residual modification of material has maximum near the threshold. (vii) Stationary regimes of ablation demonstrate change of effective activation energy with laser intensity. The model calculations are applied to Polyimide (Kapton^TM H). Here, differences in single-pulse ablated depth determined from mass loss and profilometry should be about 10 nm. Received: 16 February 1999 / Accepted: 18 February 1999 / Published online: 28 April 1999     

Gold and platinum diffusion: The key to the understanding of intrinsic point defect behavior in silicon

The study of gold and platinum diffusion is found to allow the separate observation of the intrinsic point defects, i.e., of silicon self-interstitials and of vacancies. The diffusion of gold in float zone (FZ) silicon is found to be dominated by the kick-out mechanism for temperatures of 800° C and higher. The diffusion of platinum in FZ silicon is described by the kick-out mechanism for temperatures above approximately 900° C, whereas for temperatures below approximately 850° C the dissociative mechanism governs platinum diffusion. As a result of numerical simulations, we suggest a complete and consistent set of parameters which describes the diffusion of platinum in silicon in the temperature range from 700° C to 950° C and the diffusion of gold in the temperature range from 800° C to 1100° C. The generation or recombination of self-interstitials and vacancies is found to be ineffective at least below 850° C. The concentration of substitutional platinum is determined by the initial concentration of vacancies at diffusion temperatures below 850° C. Platinum diffusion below 850°C can be used to measure vacancy distributions in silicon quantitatively.     

Dual-beam ablation of fused quartz using 266 nm and VUV lasers with different delay-times

Received: 20 August 1996/Accepted: 5 November 1996     

Comparison of scanning probe microscopies with RBS and SEM/EDX for the analysis of RuO2, TiO2 composites

2 , TiO₂) mixed oxide thin films. A digital processing of the images leads to a bipolar distribution of values of current that reflects the difference in conductivity of metallic RuO₂ and semiconducting TiO₂. The analytical results are compared with those from Rutherford backscattering spectrometry and energy dispersive X-ray imaging on these samples. STM, with digital processing of the current mapping image, shows promises for developing into a chemically sensitive probe of composite materials with nanometer spatial resolution. Received: 29 April 1997/Accepted: 4 July 1997     

Nanosecond and femtosecond excimer-laser ablation of oxide ceramics

The uv laser-ablation behavior of various oxide ceramics (Al₂O₃, MgO, ZrO₂) has been studied using different wavelengths (248 nm, 308 nm) and pulse durations (30 ns, 500 fs). Time-resolved absorption measurements of the sample and the ablation plume during ablation were performed.Using sub-ps pulses the ablation threshold fluence is generally lower than for ns pulses; the ablation rate is higher in the whole investigated fluence range up to 20 J/cm².The study of the morphology of the ablation structures and the results of the absorption experiments lead to the conclusion that different ablation mechanisms are involved. Using ns pulses plasma mediated ablation is dominating, whereas in the fs case the process is controlled by multi-photon absorption enabling microstructuring of the material.     

Influence of temperature and frequency on the electrical parameters of thermally evaporated metal-free phthalocyanine H<Subscript>2</Subscript>Pc thin films

The ac electrical properties of metal-free phthalocyanine (H₂PC) thin films have been studied in the frequency range from 10² to 2×10⁴ Hz and in the temperature range from 150 to 475 K. The ac conductivity σ was found to vary as ω^s with the index s≤1. Although these general values of s appear to be consistent with a hopping process, the present σ values do not increase monotonically with temperature. At low frequency, the capacitance and loss tangent were found to be constant over the entire frequency range, in good qualitative agreement with the equivalent circuit model consisting of an inherent capacitance in parallel with a resistive element. Moreover, at constant frequency, the two parameters increased with increasing temperature up to approximately 300 K. Above this temperature, another sharp decrease in both capacitance and loss tangent was obtained. This type of behavior was interpreted in terms of nomadic (delocalized) polarization, which leads to an increase in the dielectric constant. The drastic decrease of the capacitance and loss tangent observed above room temperature is thought to be related to the decrease in the dielectric constant, which results from the inability of the domains to hold the increases in free charge carrier concentration due to the increase of temperature. Received: 6 December 2001 / Accepted: 7 January 2002 / Published online: 19 July 2002 RID="*" ID="*"Corresponding author. Fax: +972-2/279-6960, E-mail: asaleh@science.alquds.edu     

Photocurrents in p-n Si diodes under high intensity (pulsed-laser) illumination: Quantum yields and kinetic evaluation

The photoelectric response of p-n Si photodiodes under pulsed laser illumination (half width 10 ns) at 532 nm was studied as a function of dose which was varied over 6 orders of magnitude. The photocurrent transients are dominated by a plateau-like feature due to the build up of space charge at the intensities used. Increasing bias voltage increases the height of the plateau and decreases its length. In the low-dose range the length of the transient increases linearly with dose and the collected charge (integrated current) reaches a constant value. At high doses (above 10^–5 J/pulse · cm² or 2.7×10¹³ quanta/pulse · cm²) considerable charge loss (decrease in quantum yields) is accompanied by a less than proportional increase of the transient lifetime. From model calculations the dose and voltage dependence of the quantum yield of charge collection is shown to be the result of competition between current flow and first and higher order recombination. The model calculations are consistent with experimental results. Rate constants have been obtained by fitting.