Laser-ionization mass-spectrometric studies on laser ablation of a nitrogen-rich polymer at 532 nm and 1064 nm

Laser-ionization Time-Of-Flight (TOF) mass-spectrometric studies have been carried out on the 532 nm and 1064 nm laser ablation products from a nitrogen-rich polymer. The polymer used had an elemental composition of C_6.0N_8.9H_3.4 and consisted of C=N, C-N, and N-H chemical bonds. The TOF mass spectra observed were composed of various peaks (150 amu) depending on the ablation laser wavelength. The primary peaks were assigned to C⁺, CN⁺, CHnN⁺ ₂ (n=1–3) and C₂H₂N⁺ ₃ for 532 nm ablation, and C⁺, C⁺ ₃, HCN⁺, HCCN⁺, CH₂NH⁺, HNCN⁺, H₃NCN⁺, and C₄H₄N⁺ ₇ for 1064 nm ablation. The flight velocity distributions with peak velocities ranging from 8.6×10³ cm/s to 3.8×10⁴ cm/s were measured for these products. The distinct velocity distributions observed between small and large products indicate the presence of two origins in the fragment ejection process from the polymer for both 532 nm and 1064 nm ablation. Furthermore, we suggest an importance of the translational energy of the fragments for the product generation in the laser plume.     

Dual excimer and CO2 laser etching studies of polyethylene terephthalate

Polyethylene terephthalate (PET) films preheated with a pulsed CO₂ laser have been ablatively etched with an XeCl laser. The observed reduction in ablation threshold, from 170 to 140 mJ cm^–2, is consistent with a thermal mechanism for XeCl laser ablation of PET. Transient changes in the UV absorption coefficient of PET caused by heating with pulsed CO₂ laser radiation have also been studied and a significant increase in absorption observed at 308 nm. Permanent changes in the ultraviolet absorption of PET following exposure to low fluence XeCl laser radiation are also reported.     

Laser-fluorescence diagnostics for condensation in laser-ablated copper plasmas

We are investigating the thermodynamic conditions under which condensation occurs in laser ablated copper plasma plumes. The plasma is created by XeCl excimer laser ablation (308 nm, 300 mJ/pulse) at power densities from 500–1000 MW/cm² into backing pressures of helium in the range 0–50 torr. We use laser-induced fluorescence (LIF) to probe velocity and relative density of both atomic copper and the copper dimer molecule, Cu₂, which is formed during condensation onset. At low pressure (10 mtorr), the atomic Cu velocity peaks at approximately 2×10⁶ cm/s. Copper dimer time-of-flight data suggest that condensation onset occurs after the Cu atoms have slowed very significantly. Excitation scans of the Cu₂A-X (0,0) and (1,1) bands yield a rotational and vibrational temperature in the neighborhood of 300 K for all conditions studied. Such low temperatures support the theory that Cu₂ is formed under thermally and translationally cold conditions. Direct laser beam absorption is used to determine the number density of atomic copper. Typical densities attained with 5 torr of helium backing gas are 6–8×10¹³ cm^–3. Rayleigh scattering from particulate is easily observable under conditions favorable to particulate production.     

Selective ablation of thin SiO<Subscript>2</Subscript> layers on silicon substrates by femto- and picosecond laser pulses

The selective ablation of thin (∼100 nm) SiO₂ layers from silicon wafers has been investigated by applying ultra-short laser pulses at a wavelength of 800 nm with pulse durations in the range from 50 to 2000 fs. We found a strong, monotonic decrease of the laser fluence needed for complete ablation of the dielectric layer with decreasing pulse duration. The threshold fluence for 100% ablation probability decreased from 750 mJ/cm² at 2 ps to 480 mJ/cm² at 50 fs. Significant corruption of the opened Si surface has been observed above ∼1200 mJ/cm², independent of pulse duration. By a detailed analysis of the experimental series the values for melting and breaking thresholds are obtained; the physical mechanisms responsible for the significant dependence on the laser pulse duration are discussed.     

Ultraviolet photoablation of a plasma-synthesized fluorocarbon polymer

Plasma polymerized tetrafluoroethylene (PPTFE) is shown to undergo efficient 248 nm excimer laser ablation. The principle difference between this material and the analogous polytetrafluoroethylene (PTFE), which results in only poor quality ablation, is PPTFE's much greater absorption coefficient (7×10⁴ vs. 10² cm^–1). A plot of the ablation depth per pulse versus incident fluence indicates that the threshold for significant ablation occurs near 50 mJ/cm², and that approximately 0.7 m/pulse can be removed at 800 mJ/cm². Near threshold, the ablation rate curve can be fit by a single Arrhenius-type exponential. This suggests that the removal process is at least partially governed by a photothermal process, similar to well-known laser induced thermal desorption experiments. In the very low fluence regime between 10 and 30 mJ/cm², small removal rates are measured in a process likely dominated by non-thermal ablation. The paper concludes with a discussion of the high quality, micron-size features that can be directly patterned into PPTFE surfaces.     

Pulsed UV-laser-induced chemistry of perfluoropolyether lubricant film

We investigate the molecular structure change of laser-irradiated perfluoropolyether lubricant on disk media by using mass spectroscopy. A KrF excimer laser with a wavelength of 248 nm was used to irradiate the lubricant film (2 nm) on a carbon overcoat surface. We found that two unique mass peaks emerged from the laser-irradiated lubricant mass spectra, which are attributed to OH-CHF-O(:H⁺)-CHF-OH and F-COO-CF₂-CF₂-CF₂-CF₂ ⁺ respectively. When thelaser fluence increases to 100 mJ/cm², these two unique mass peaks start to be enhanced drastically while the abundance of the end group of the lubricant, CF₂CH₂OH, remains almost constant, indicating that the two unique species are generated from the scission and re-arrangement of the backbone ether chains. With a laser fluence beyond 140 mJ/cm², the disk media surface damage is observable and lubricant evaporation is the main pathway. Received: 24 October 2001 / Accepted: 3 December 2001 / Published online: 3 May 2002     

R branch tuning characteristics of the13CH3F Raman FIR laser

Summary We described a¹³CH₃F Raman laser pumped by a grating tuned 20 atmospheres CO₂ laser. The emission characteristics of the¹³CH₃F laser extends from 14 cm^–1–35 cm^–1 and from 49 cm^–1–72 cm^–1; about 65% of these frequency ranges can be covered with tunable radiation. The characteristics shows a strong dependence on the rotaional quantum numbers of the states involved in the Raman laser transitions and, within each tuning interval, on the frequency offset with respect to the frequencies of resonant transitions. We obtained, at 51 cm^–1, a maximum FIR laser pulse energy of about 800 J (at a pump energy of 200 mJ), corresponding to a photon conversion of about 8%. In some cases we have observed simultaneous emission at a Raman and a cascade frequency. In addition, FIR emission power dependence on¹³CH₃F gas pressure and pump pulse power were investigated for different J quantum numbers.     

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.     

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.     

Femtosecond-pulse laser ablation of human corneas

A femtosecond pulse laser in the visible spectral region shows promise as a potentially new powerful corneal sculpting tool. It combines the clinical and technical advantages of visible wavelengths with the high ablation quality observed with nanosecond-pulse excimer lasers at 193 nm. A femtosecond and a nanosecond dye laser with pulse durations of 300 fs and 7 ns, and centre wavelengths at 615 nm and 600 nm, respectively, both focused to an area of the order of 10^–5 cm², have been applied to human corneal ablation. Nanosecond laser pulses caused substantial tissue disruption within a 30–100 m range from the excision edge at all fluences above the ablation threshold of F _th60 J cm^–2 (I _th9 GW cm^–2). Completely different excisions are produced by the femtosecond-pulse laser: high quality ablations of the Bowman membrane and the stroma tissue characterised by damage zones of less than 0.5 m were observed at all fluences above ablation threshold of F _th1 J cm^–2 or I _th3 TW cm^–2 (3×10¹² W cm^–2). The transparent cornea material can be forced to absorb ultrashort pulses of extremely high intensity. The fs laser generates its own absorption by a multiphoton absorption process.     

XeCl laser ablation of polyetheretherketone

Ablation of polyetheretherketone (PEEK), a high temperature thermoplastic, by XeCl laser radiation occurs at fluences in excess of 0.07±0.01 J cm^–2. The volatile products of ablation are CO and C₂H₂ with smaller quantities of CH₄, C₄H₂, C₆H₆ and other C₃ and C₄ hydrocarbons. At fluences close to the threshold ablation produces involatile material of relatively high molecular weight but at high fluences extensive disruption of the PEEK structure occurs with conversion of all of the oxygen in the polymer to carbon monoxide.     

Ablation process of silica glass induced by laser plasma soft X-ray irradiation

Silica glass can be machined by irradiation with laser plasma soft X-rays on nano- and micrometer scale. We have investigated the ablation process of silica glass induced by laser plasma soft X-ray irradiation. We observed ionic and neutral species emitted from silica surfaces after irradiation. Dominant ions and neutrals are O⁺ and Si⁺ ions and Si, O, SiO and Si₂ neutrals, respectively. The ions have kinetic energies of 13 and 25 eV, which are much higher than those of particles emitted by evaporation. The energy of laser plasma soft X-rays absorbed to silica glass at a fluence of 1.4 J/cm² is estimated to be 380 kJ/cm³, which is higher than the binding energy of SiO₂ of 76 kJ/cm³. These results suggest that the most of the bonds in silica glass are broken by absorption of laser plasma soft X-rays, that several percent of the atoms are ionized, and that neutral atoms are emitted together with repulsive ions. The process possibly enables us to fabricate nano structures.     

Nitrogen atom detection in low-pressure flames by two-photon laser-excited fluorescence

Nitrogen atoms have been detected in stoichiometric flat premixed H₂/O₂/N₂ flames at 33 and 96 mbar doped with small amounts of NH₃, HCN, and (CN)₂ using two-photon laser excitation at 211 nm and fluorescence detection around 870 nm. The shape of the fluorescence intensity profiles versus height above the burner surface is markedly different for the different additives. Using measured quenching rate coefficients and calibrating with the aid of known N-atom concentrations in a discharge flow reactor, peak N-atom concentrations in these flames are estimated to be on the order of 10¹²–5×10¹³ cm^–3; the detection limit is about 1×10¹¹ cm^–3.     

Micromachining of a thin film by laser ablation using femtosecond laser with masks

A gold thin film was machined by laser ablation using a femtosecond laser with mask patterns in the shape of lines and numbers. The patterns were successfully transferred with proper focusing and laser fluence. The optimal femtosecond laser fluence to keep the line width was about 5.2 mJ/cm² on the mask, and 99 mJ/cm² on the film. The processing resolution was 13 μm, and the narrowest line width was about 4 μm.     

Deposition of potassium-oxygen on silicon surfaces by pulsed laser ablation of potassium superoxide: Study of work function changes

Potassium-oxygen species were deposited on pure, Si nanoparticles coated and H-terminated Si nanoparticles coated p-Si(1 0 0) surfaces by pulsed laser ablation of potassium superoxide (KO₂) target. The deposition properties, composition and the work function changes of the deposited species were investigated in situ using an X-ray photoelectron spectroscopy (XPS) and a Kelvin probe measurement. The deposited species were assigned to K₂O₂ and KO₂, and they can be selectively deposited by controlling the laser fluence: i.e., at 200 mJ/cm² and at those more than 300 mJ/cm², respectively. Experimental results showed that the work function decreased drastically with depositing of KO_x (x = 1 or 2), and the minimum work function values observed were 1.0 eV and 0.7 eV for pure p-Si(1 0 0) and Si nanoparticles coated substrates, respectively. The study demonstrates the formation of the surface species with minimum work function can be identified by XPS.     

Short-pulse UV laser ablation of solid and liquid metals: indium

2 to 2.5 mJ/cm² when a 0.5 ps pulse is used instead of a 15 ns laser pulse. Measurements on liquid indium show a different behavior. With 15 ns laser pulses the threshold fluence is lowered by a factor of ∼3 from 100 mJ/cm² for solid indium to 30 mJ/cm² for liquid indium. In contrast, measurements with 0.5 ps laser pulses do not show any change in the ablation threshold and are independent of the phase of the metal at 2.5 mJ/cm². This behavior could be explained by thermal diffusion and heat conduction during the laser pulse and demonstrates in an independent way the energy lost into the material when long laser pulses are applied. Time-of-flight measurements to investigate the underlying ablation mechanism show thermal behavior of the ablated indium atoms for both ps and ns ablation and can be fitted to Maxwell-Boltzmann distributions. Received: 2 December 1996/Accepted: 11 December 1996     

Generation of CdS clusters using laser ablation: the role of wavelength and fluence

The formation of cationic clusters in the laser ablation of CdS targets has been investigated as a function of wavelength and fluence by mass spectrometric analysis of the plume. Ablation was carried out at the laser wavelengths of 1064, 532, 355, and 266 nm in order to scan the interaction regimes below and above the energy band gap of the material. In all cases, the mass spectra showed stoichiometric Cd _n S _n ⁺ and nonstoichiometric Cd _n S _n−1⁺, Cd _n S _n+1⁺, and Cd _n S _n+2⁺ clusters up to 4900 amu. Cluster size distributions were well represented by a log-normal function, although larger relative abundance for clusters with n=13, 16, 19, 34 was observed (magic numbers). The laser threshold fluence for cluster observation was strongly dependent on wavelength, ranging from around 16 mJ/cm² at 266 nm to more than 300 mJ/cm² at 532 and 1064 nm. According to the behavior of the detected species as a function of fluence, two distinct families were identified: the “light” family containing S₂⁺ and Cd⁺ and the “heavy” clusterized family grouping Cd₂⁺ and Cd _n S _m ⁺. In terms of fluence, it has been determined that the best ratio for clusterization is achieved close to the threshold of appearance of clusters at all wavelengths. At 1064, 532, and 355 nm, the production of “heavy” cations as a function of fluence showed a maximum, indicating the participation of competitive effects, whereas saturation is observed at 266 nm. In terms of relative production, the contribution of the “heavy” family to the total cation signal was significantly lower for 266 nm than for the longer wavelengths. Irradiation at 355 nm in the fluence region of 200 mJ/cm² has been identified as the optimum for the generation of large clusters in CdS.     

Effects of laser irradiation energy density on the properties of pulsed laser deposited ITO thin films

The properties of indium tin oxide (ITO) thin films, deposited at room temperature by simultaneous pulsed laser deposition (PLD), and laser irradiation of the substrate are reported. The films were fabricated from different Sn-doped In₂O₃ pellets at an oxygen pressure of 10 mTorr. During growth, a laser beam with an energy density of 0, 40 or 70 mJ/cm² was directed at the middle part of the substrate, covering an area of ∼1 cm². The non-irradiated (0 mJ/cm²) films were amorphous; films irradiated with 40 mJ/cm² exhibited microcrystalline phases; and polycrystalline ITO films with a strong 〈111〉> preferred orientation was obtained for a laser irradiation density of 70 mJ/cm². The resistivity, carrier density, and Hall mobility of the ITO films were strongly dependent on the Sn doping concentration and the laser irradiation energy density. The smallest resistivity of ∼1×10^-4 Ω cm was achieved for a 5 wt % Sn doped ITO films grown with a substrate irradiation energy density of 70 mJ/cm². The carrier mobility diminished with increasing Sn doping concentration. Theoretical models show that the decrease in mobility with increasing Sn concentration is due to the scattering of electrons in the films by ionized centers. PACS 81.15.Fg; 73.61.-r; 73.50.-h     

Tuning characteristics of a high pressure CO2 laser pumped CH3F Raman laser

Conclusion We described a CH₃F Raman laser pumped by a two stage 20 atmospheres CO₂ laser. The emission spectrum of the CH₃F laser at 11 Torr extends from 23 cm^–1 to 45 cm^–1 when the CO₂ laser is scanned over the 9R emission branch at a fixed pump power of 180 mJ. The emission spectrum shows a strong structure with large parts where the FIR energy decreases to zero. This fact makes the use of such a laser for spectroscopic scanning experiments in the FIR difficult. The laser is, however, very suited for working at fixed but adjustable FIR frequencies. The pulse energy in the maxima of the emission characteristics at a pump energy of 180 mJ exceeds 300 J, which corresponds a photon conversion coefficient of more than 6%.     

Picosecond laser ablation of thin copper films

The ablation process of thin copper films on fused silica by picosecond laser pulses is investigated. The ablation area is characterized using optical and scanning electron microscopy. The single-shot ablation threshold fluence for 40 ps laser pulses at 1053 nm has been determinated toF _thres = 172 mJ/cm². The ablation rate per pulse is measured as a function of intensity in the range of 5 × 10⁹ to 2 × 10¹¹ W/cm² and changes from 80 to 250 nm with increasing intensity. The experimental ablation rate per pulse is compared to heat-flow calculations based on the two-temperature model for ultrafast laser heating. Possible applications of picosecond laser radiation for microstructuring of different materials are discussed.