Excimer UV lamp irradiation induced grafting on synthetic polymers

Surface modifications on polyethyleneterephthalate (PET) films following excimer UV lamp irradiation induced grafting were studied. Characteristics of the modifications depending on the conditions during the irradiation were analysed using contact-angle measurements, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), differential scanning calorimetry (DSC) and Fourier-transform infrared spectroscopy (FTIR). Depending on the conditions during the irradiation different surface modifications were obtained, which can generally be classified regarding the hydrophilic or hydrophobic characteristics of the resulting surface. It is shown that not every substance that meets the general demands will be grafted on synthetic polymers using excimer UV radiation. Examples of agents that can simply be grafted onto polymer surfaces and those that undergo further crosslinking, building up thin films are listed. Agents used for grafting on polymers are 1,5-hexadiene, perfluoro-4-methyl-pent-2-ene, polyethyleneglycol 200, monosilane and polyethylene. The transferability of the effects achieved to substrates such as polyparaphenylene terephthalamide or polymetaphenylene isophthalamide is shown. Received: 23 June 2000 / Accepted: 28 June 2000 / Published online: 5 October 2000     

Influence of electric field on heterogeneous reactions stimulated by laser light

We present experimental data for vanadium and copper oxidation by cw CO₂ laser light in an external electric field. Direct influence of the external field on the crystallisation process has been demonstrated in both vanadium and copper cases; the oxidation rate and surface morphology depend sensitively on the sign and strength of the external field.     

Photochemical surface modification of PET by excimer UV lamp irradiation

UV irradiation has interesting potential for the photochemical modification of polymers. In order to study cross-linking effects and/or thin-layer deposition following a treatment in the presence of bi-functional media or in inert atmosphere, irradiation of PET in various atmospheres was performed using a KrCl excimer lamp. Surface properties were investigated by atomic force microscopy, nanoindentation, micro-thermal analysis, and X-ray photo-electron spectroscopy. The studies reveal that surface chemical composition, morphology, adhesion, thermomechanics, and stiffness/modulus are strongly affected by UV irradiation in the presence of bi-functional media. Films treated in octadiene and argon show an increase of surface modulus, much less expansion, and lower soft/melt temperatures, which is an indication of the surface cross-linking effect and a decrease of crystallinity within the near-surface layer. In the case of a diallylphthalate-treated film, depending on the local structure, either a strong decrease of melting temperature or no melting point is found, which is attributed to the irregular cross linking and thickness of the modified layer associated with a decrease of surface modulus. A significant increase of the alkali resistance is found after irradiation, as a result of both wetting and cross-linking effects on the polymer surface.     

Generation of submicron surface gratings on LiNbO3 by ultrashort UV laser pulses

3 by short ultraviolet laser pulses (0.5 ps, 248 nm) is presented. Gratings with a period of 360 nm and a modulation depth of 80 nm are fabricated on the sample surface by single-laser-shot exposure. The structures are projection imaged by a Schwarzschild objective in air. The modulation depth can be varied by applying multiple-pulse exposure. Received: 18 July 1997/Accepted: 5 August 1997     

Depth profiling a III–V multilayered structure with an excimer laser

A multilayered structure of GaAs and AlGaAs was depth profiled using the technique of digital etching. A single excimer laser (KrF) was used to control the etch rate and to identify each layer by monitoring the Ga ions generated during the desorption process. The Ga ions were the only ions observed and were only generated when the photon flux was in the GaAs layer. The etch rate, 0.9 monolayers (2.5 Å) per pulse, was constant with depth. The overall layer recognition resolution was 45 monolayers.     

Bubble nucleation and pressure generation during laser cleaning of surfaces

with a pressure pulse width of . Additionally, the phase of an acoustic pulse is observed to change upon reflection at the liquid–solid interface if bubbles are present, providing a direct proof for laser-induced bubbles. Received: 5 December 1996/Accepted: 6 January 1997     

Removal of oxygen atoms from a SiO2 surface by incoherent vacuum ultraviolet excimer irradiation

We have demonstrated the non-thermal removal of oxygen atoms from an oxidized silicon surface (SiO₂) on a silicon wafer by the use of a low-power (0.3 mW cm^-2) incoherent vacuum ultraviolet (VUV) light source at 126 nm. X-ray photoelectron spectroscopy (XPS) has shown that a maximum Si concentration of 80% appears at the surface after a 20-h irradiation with 9.8 eV photons, as a result of oxygen removal from the SiO₂ matrix. The surface morphology, however, indicates no damage or melting on the surface even after the irradiation. Received: 15 April 2002 / Accepted: 17 April 2002 / Published online: 10 September 2002 RID="*" ID="*"Permanent address: Nano-Tech Photon Inc., Shimotomita 4132-1, Shintomi, Miyazaki, 889-1404, Japan RID="**" ID="**"Corresponding author. Fax: +81-985/583-899, E-mail: kubodera@opt.miyazaki-u.jp     

Laser-assisted etching of gallium arsenide in chlorine at 308 nm

Xenon chloride (308 nm) excimer laser-assisted etching of GaAs (100) in Cl₂ was demonstrated and characterized with respect to laser and gas parameters. The etch rate increased linearly with laser fluence from thresholds in the range of 50 to 75 mJ/cm² to the highest fluence studied, 650 mJ/cm². For a laser fluence of 370 mJ/cm², the etch rate varied with Cl₂ pressure reaching a maximum at a Cl₂ pressure of about 2 Torr. The etch rate decreased monotonically with Ar buffer gas pressure because of redeposition of GaCl₃ products into the etched channel. The redeposited GaCl₃ affected the etch rate and the etch morphology. The etch rate and morphology also varied with laser repetition rate. The mobility of chlorine on the surface also plays an important role in the etching mechanism.     

UV desorption and photochemistry of dimethylgold hexafluoroacetylacetonate adsorbed on a quartz substrate

The photodesorption and photodecomposition pathways of dimethylgold hexafluoroacetylacetonate, DMG (hfac), adsorbed on a cooled quartz substrate is reported for 222-nm KrCl excimer laser radiation. The time-of-flight (TOF) of neutral photoproducts, desorbed from the surface of the gold film formed during the experiment, were analyzed under collisionless conditions by a differentially-pumped mass spectrometer. Extensive dissociation of adsorbed DMG (hfac) into DMG and the hfac ligand was observed. The ligand was found to recombine with a CH₃ radical on the surface. Translational energy distributions for the detected species were obtained by deconvoluting the TOF curves into a self-consistent set of Maxwell-Boltzmann distributions for the desorbed parent molecule, laser-induced decomposition products, and surface recombination reaction products. The implications of these results for the mechanistic details of the low-pressure, laser-assisted organometallic deposition of DMG(hfac) are discussed.ONT/NRL Research Associate (Nov. 1987-Oct. 1988)NRC/NRL Cooperative Research Associate     

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     

Sulfur-modified surface of InP(001): Evidence for sulfur incorporation and surface oxidation

Received: 21 March 1997/Accepted: 12 August 1997     

Absorption changes under UV illumination in doped PMMA

The absorption spectra of poly(methyl methacrylate) (PMMA) doped with the photoinitiator 2,2-dimethoxy-2-phenylacetophenone (DMPA) change under illumination with UV light. Time-resolved measurements of the kinetics of the absorption changes at 352 nm prove the existence of a second light-induced reaction besides the expected light-induced decay of the photoinitiator. We propose a model for this second process which is in good agreement with the observed experimental facts. Received: 17 July 2000 / Published online: 5 October 2000     

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     

Ablation of polyethylene terephthalate at 266 nm

Microstructures of micrometer sizes are produced on the surface of polyethylene terephthalate using nanosecond Nd:YAG-laser irradiation at 266 nm wavelength. The stable and well-defined structures were investigated using scanning electron microscopy. A theoretical model is suggested for the nonlinear behavior of etch depth versus incident laser fluence. In this model, two-photon stepwise absorption of chromophores is the dominant mechanism. Received: 3 August 2000 / Accepted: 9 January 2001 / Published online: 25 July 2001     

Infrared multiple photon decomposition of CHBrF2 induced by a free-electron laser

2 . The laser generates an intense infrared macropulse with a duration of 17 μs; the macropulse consists of a train of 380 micropulses, each of which has a duration of a few picoseconds. The fluence of a macropulse was estimated to be about 16 Jcm^-2 at a beam waist. Peak wavelengths were set in the range of 9–10 μm. The macropulse induced the IRMPD of 1 and 5 Torr CHBrF₂; most of molecules in the focal region seemed to decompose at a wavelength of 9.3 μm. The mechanism is the initial decomposition of CHBrF₂ to CF₂ and HBr, followed by the dimerization of CF₂ to form C₂F₄. The decomposition was found to be isotopically selective at 9.7 μm; the final product C₂F₄ had a ¹³C atomic fraction of 6%. Th e addition of CO₂ to CHBrF₂ significantly decreased the yield of C₂F₄. vibrationally excited CHBrF₂ molecules produced by laser pulses were efficiently deactivated by CO₂ molecules. Received: 7 October 1996     

Surface chemistry of Zn3P3 single crystals studied by XPS

X-ray photoemission spectroscopy (XPS) has been used to study the surface reaction of Zn₃P₂ single crystals.The spectra of crystals exposed to H₂, O₂, CO₂, O₂+H₂O or CO₂+H₂O during a four week period were compared to the spectra of as-grown or in UHV scraped samples. For samples contaminated with the wet gases O₂+H₂O and CO₂+H₂O additional phosphorus core levels together with a shift of the zinc core levels were observed. For crystals exposed to atmosphere during several months no phosphorus could be detected on the gasgrown surface, whereas the stochiometry of Zn₃P₂ was maintained within the bulk. Crystals with scraped surfaces showed no moisture sensitivity. No surface contamination was also detected for Zn₃P₂ crystals deposited with up to 1000 L H₂O or exposed to atmosphere during 30 min.     

Lead films produced by laser vapor deposition

The deposition of lead film on quartz substrates by photolysing tetraethyl lead vapor with a laser is reported. The dependence of the deposition rate on the pressure of tetraethyl lead, on the light intensity and on the pressure of the buffer gas is measured. Deposition phenomena at low light intensity are discussed.     

Large area excimer laser induced deposition of titanium from titanium tetrachloride

Large area excimer laser induced deposition of titanium on fused silica from TiCl₄ is studied with an emphasis on process modeling. We show that several TiCl₄ monolayers can be adsorbed if the surface is adequately prepared and that the Ti thin film growth occurs through the photodecomposition of this adsorbed TiCl₄ layer. We propose two growth regimes. During an initiation phase, up to 3 nm in thickness, the adsorbed layer is photochemically decomposed giving a growth rate of 0.015 nm/pulse. In a second phase, the deposition rate increases to between 2 and 7 nm/pulse due to the laser heating of the preceding photochemically deposited titanium film. Between consecutive pulses, TiCl₄ molecules primarily from the adsorbed layer diffuse to the reaction zone leading to a new adsorbed layer ready to be transformed to solid titanium.     

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.