Energy efficiency of femtosecond laser ablation of polymer materials

We present the results of an experimental study of the ablation spectral energy thresholds for a number of polymer materials ((C₂F₄) _n , (CH₂O) _n ) exposed to femtosecond (τ_0.5 ~ 45–70 fs) laser pulses (λ ~ 266, 400, 800 nm) under atmospheric conditions and under vacuum (p ~ 10–2 Pa). We have analyzed the energy thresholds and the efficiency of optical, thermophysical, and gasdynamic processes in laser ablation vs. the laser pulse duration and photon energy.     

Study of opto-mechanical characteristics of interaction of ultrashort laser pulses with polymer materials

The opto-mechanical characteristics, such as the specific mechanical recoil momentum, the specific impulse, and the energy efficiency, of the laser ablation of flat polymer targets ((C₂F₄) _n , (CH₂O) _n ) have been determined experimentally for the first time for the case of excitation with femtosecond pulses (τ ∼ 45–70 fs) of UV-IR (λ ∼ 266, 400, 800 nm) laser radiation (I ₀ up to 10¹⁵ W/cm²) under normal atmospheric and vacuum (p ∼ 10⁻⁴ mbar) conditions. The efficiency of mechanical recoil momentum generation is analyzed for various regimes of the laser irradiation.     

Experimental study of optical gas-dynamic processes of polymeric material ablation by ultrashort laser pulses

Optical gas-dynamic processes occurring in polymeric targets ((CH₂O) _n , (C₂F₄) _n ) exposed to ultrashort laser pulses (τ _0.5 ∼ 45 − 70 fs; λ _I,II,III = 266, 400, 800 nm; and E/S ∼ 0.1 − 40 J/cm² at r ₀ ∼ 20 μm) were studied under normal conditions and in vacuum (p ∼ 10⁻² Pa). The dynamics of the mass flow from the target surface (m′ ∼ 10⁻⁵ − 10⁻⁴ g/J) was studied and the spectral-energy thresholds of laser ablation, the electron density distribution (n _e ∼ 10¹⁴ − 10¹⁸ cm⁻³), the mass-averaged velocity of the material flow from the target surface (∼ 10³ m/s), and the chemical composition and average temperature in the near-surface plasma formation (T ∼ 5000 K) were determined using interference microscopy, emission spectroscopy, and shadowgraphy.     

Dynamics of femtosecond-laser-ablated liquid-aluminum nanoparticles probed by means of spatiotemporally resolved X-ray absorption spectroscopy

We investigated spatiotemporal evolution of expanding ablation plume of aluminum created by a 100-fs, 10¹⁴–10¹⁵-W/cm² laser pulse. For diagnosing dynamic behavior of ablation plume, we employed the spatiotemporally resolved X-ray absorption spectroscopy (XAS) system that consists of a femtosecond-laser-plasma soft X-ray source and a Kirkpatrick–Baez (K–B) microscope. We successfully assigned the ejected particles by analyzing structure of absorption spectra near the L _II,III absorption edge of Al, and we clarified the spatial distribution of Al⁺ ions, Al atoms, and liquid droplets of Al in the plume. We found that the ejected particles strongly depend the irradiated laser intensity. The spatial distribution of atomic density and the expansion velocity of each type of particle were estimated from the spatiotemporal evolution of ablation particles. We also investigated a temperature of the aluminum fine particles in liquid phase during the plume expansion by analyzing the slope of the L _II,III absorption edge in case of 10¹⁴-W/cm² laser irradiation where the nanoparticles are most efficiently produced. The result suggests that the ejected particles travel in a vacuum as a liquid phase with a temperature of about 2500 to 4200 K in the early stage of plume expansion.     

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     

Formation of a plane layer of plasma under irradiation by a soft X-ray source

We investigate theoretically the formation of a plasma in a plane layer of polymer foam (density ρ = 0.002 g/cm³ and thickness 800 μm) under the action of an external source of soft X-ray radiation under the conditions of PHELIX experiments. The incident flux is assumed to have a Planck’s distribution over the spectrum with T _rad = 20–40 eV. In numerical calculations, the flux of incident X-ray radiation and the spectral constants of the target substance are varied. The action of an external X-ray radiation source on a low-density foam substance with a density of 2 mg/cm³ causes a plasma to be formed with relatively homogeneous profiles of density and temperature T = 15–35 eV. Absorption of externalradiation energy is distributed in the volume. The plasma temperature increases with increase in the external energy, and the energy passed through the plasma also increases. The results prove to be sensitive to the values of optical constants used in numeral simulation. The spectral flux of external radiation passed through the plasma is chosen as a criterion of correctness of the optical constants used in the calculations. In future experiments using the PHELIX facility, we plan to investigate the slowing-down of an ion beam in a plasma formed as a result of indirect heating of low-density polymer triacetate cellulose (TAC) foam with densities ρ = 0.001–0.01 g/cm³ under the action of a pulse of X-ray radiation, into which the laser radiation is preliminarily transformed.     

Chemical, morphological and chromatic behavior of mural paintings under Er:YAG laser irradiation

Several pigments (malachite CuCO₃⋅Cu(OH)₂, azurite 2CuCO₃⋅Cu(OH)₂, yellow ochre (goethite α-FeOOH, gypsum CaSO₄⋅2H₂O), St. John’s white CaCO₃ formed from slaked lime) and respective mural paintings specimens were subjected to the free-running Er:YAG laser radiation in order to study their damage thresholds, in a broad range of laser fluences, both in dry and wet conditions. The specimens’ damage thresholds were evaluated by spectroscopic methods, colorimetric measurements and microscopic observation. The pigments containing –OH groups were found to be more sensitive than St. John’s white; hence the most sensitive paint layers in dry conditions are those containing malachite, azurite (both 1.3 J/cm²) and yellow ochre (2.5 J/cm²) as compared to the ones containing St. John’s white (15.2 J/cm²). The presence of wetting agents (w.a.) attenuated the pigments chemical alteration. The damage thresholds of all the paint layers, in presence of w.a., were found to be around 2.5 J/cm². The alteration was caused by thermo-mechanical damage and by binding medium ablation of a fresco and a secco prepared specimens, respectively.     

Structure and optical properties of carbon films obtained by multipulse pulsed laser deposition

We have obtained carbon thin films on silicon and glass substrates with multipulse pulsed laser irradiation of graphite under vacuum (p ≈ 2.6 Pa) using a high-frequency series of nanosecond laser pulses (τ = 85 ns, λ = 1060 nm) with pulse repetition frequency f ≈ 10–20 kHz and laser power density q ≈ 15–40 MW/cm². We established the optimal laser power density and laser pulse repetition frequency for obtaining amorphous nanostructured diamond-like films.     

Characterization of excimer laser ablation generated pepsin particles using multi-wavelength photoacoustic instrument

Preparation of organic thin layers on various special substrates using the pulsed laser deposition (PLD) technique is an important task from the point of view of bioengineering and biosensor technologies. Earlier studies demonstrated that particle ejection starts during the ablating laser pulse resulting in significant shielding effects which can influence the real fluence on the target surface and consequently the efficiency of layer preparation. In this study, we introduce a photoacoustic absorption measurement technique for in-situ characterization of ablated particles during PLD experiments. A KrF excimer laser beam (λ=248 nm, FWHM=18 ns) was focused onto pepsin targets in a PLD chamber; the applied laser fluences were 440 and 660 mJ/cm². We determined the wavelength dependence of optical absorption and mass specific absorption coefficient of laser ablation generated pepsin aerosols in the UV–VIS–NIR range. On the basis of our measurements, we calculated the absorbance at the ablating laser wavelength, too. We demonstrated that when the laser ablation generated pepsin aerosols spread through the whole PLD chamber the effect of absorptivity is negligible for the subsequent pulses. However, the interaction of the laser pulse and the just formed particle cloud generated by the same pulse is more significant.     

Near IR laser light visualizators using nonlinear GaSe and other layered crystallites

Two methods of preparation of the devices for visualization of pulsed and continuous near-IR (near infrared) are described and the results of conversion of pulsed and continuous IR (800–1360 nm) laser radiation into the visible range of spectra (400–680 nm) by using a transparent substrate covered with the particles (including nanoparticles) of effective nonlinear materials of GaSe _x S_{1 − x} (0.2 ≤ x ≤ 0.8) are presented. Converted light can be detected in transmission or reflection geometry as a visible spot corresponding to the real size of the incident laser beam. Developed device structures can be used for checking if the laser is working or not, for optical adjustment, for visualization of distribution of laser radiation over the cross of the beam and for investigation of the content of the laser radiation. Low energy (power density) limit for visualization of the IR laser pulses with 2–3 ps duration for these device structures are: between 4.6–2.1 μJ (3 × 10⁻⁴−1 × 10⁻⁴ W/cm²) at 1200 nm; between 8.4–2.6 μJ (4.7 × 10⁻⁴−1.5 × 10⁻⁴ W/cm²) at 1300 nm; between 14.4–8.1 μJ (8.2 × 10⁻⁴–4.6 × 10⁻⁴ W/cm²) at 1360 nm. Threshold damage density is more than 10 MW/cm² at λ = 1060 nm, pulse duration τ = 35 ps. The results are compared with commercially existing laser light visualizators.     

Narrow resonances of two-photon absorption of super-narrow pulses in a gas

First cw laser oscillation with thresholds below 1 mW was observed for various B¹П_u → X¹ ∑ _g ⁺ transitions of diatomic molecular sodium excited by different argon laser lines in the range of 454–488 nm. For pump powers of 0.5 W output powers up to 3 mW and single-pass gain up to 0.1 cm⁻¹ were obtained. Some properties of the heat pipe laser system are discussed.     

Laser on nitrogen-electronegative gas mixtures, pumped by inductive energy storage generator: Experiment and theoretical model

The advantages of inductive energy storage (IES) generators for increasing the pulse energy, power, and duration for nitrogen laser pumped by self-sustained transverse discharge have been experimentally demonstrated. A theoretical model is developed and the operation of IES-pumped laser on nitrogen-electronegative gas mixtures is numerically simulated. It is shown experimentally and theoretically that, adding electronegative gases, one can control the pulse shape of lasing on the C³II _u -B³II _g transition in nitrogen. The increase in the electric field strength in the laser gap in N₂-NF₃ and N₂-SF₆ mixtures produced 337.1-nm laser pulses consisting of two spaced peaks and 40–50-ns pulses close to rectangular. The increase in the laser active volume to 6 l (discharge cross section to 6×10 cm²) in N₂–SF₆ mixtures made it possible to obtain the maximum output energy (Q=110 mJ) and UV power (P _las =6 MW). In N₂-NF₃ mixtures, the laser pulse duration was up to ∼100 ns with an energy up to Q=30 mJ.     

Picosecond laser ablation of SiO2 layers on silicon substrates

In this work, we report on laser ablation of thermally grown SiO₂ layers from silicon wafer substrates, employing an 8–9 ps laser, at 1064 (IR), 532 (VIS) and 355 nm (UV) wavelengths. High-intensity short-pulse laser radiation allows direct absorption in materials with bandgaps higher than the photon energy. However, our experiments show that in the intensity range of our laser pulses (peak intensities of <2×10¹² W/cm²) the removal of the SiO₂ layer from silicon wafers does not occur by direct absorption in the SiO₂ layer. Instead, we find that the layer is removed by a “lift off” mechanism, actuated by the melting and vaporisation of the absorbing silicon substrate. Furthermore, we find that exceeding the Si melting threshold is not sufficient to remove the SiO₂ layer. A second threshold exists for breaking of the layer caused by sufficient vapour pressure. For SiO₂ layer ablation, we determine layer thickness dependent minimum fluences of 0.7–1.2 J/cm² for IR, 0.1–0.35 J/cm² for VIS and 0.2–0.4 J/cm² for UV wavelength. After correcting the fluences by the reflected laser power, we show that, in contrast to the melting threshold, the threshold for breaking the layer depends on the SiO₂ thickness.     

Fragmentation of the POPOP molecule by electron-impact ionization

Single and dissociative ionizations of the POPOP molecule by electron impact in the gas phase are studied using mass spectroscopy. Fragmentation pathways of the molecule are proposed taking into account the common system of conjugated π-electrons and heteroatoms in the POPOP molecule. The appearance thresholds for certain fragments of the molecule are determined based on experimentally measured ionization cross sections as functions of the ionizing electron energy. An ion with m/z = 144 [C₉H₆ON]⁺ that is complementary to a fragment with m/z = 220 [C₁₃H₁₀ON]⁺ (present in the NIST mass spectrum database) is found for the first time in the mass spectrum of POPOP. Its appearance threshold is determined (E_ap = 9.48 eV). __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 4, pp. 482–489, July–August, 2008.     

CdS plume composition and dynamics of neutral species upon ablation with 532 nm laser light

The neutral species present in CdS ablation plumes upon nanosecond 532 nm laser irradiation at a moderate fluence of 0.5–0.75 J cm⁻² have been studied. Neutral Cd _n S _m clusters have been identified, some as large as (CdS)₃₃₋₃₄ (1–2 nm in diameter). The analysis of the dynamics of neutral species shows an expansion with two components that differ both in composition and dynamics. A fast, high kinetic energy component, dominated by S₂ which acquires free-flow conditions at short distances from the target, is followed by a slower component characterized by similar speeds for all species. This slower component shows dynamic features that are expected to favor aggregation processes leading to effective cluster formation.     

Luminescence and lasing properties of neodymium- and uranium-activated inorganic laser liquids

An attempt was made to describe and show the possibilities of new inorganic neodynium- and uranium-activated laser liquids: SO₂-GaCl₃-NdCl₄; SO₂Cl₂-GaCl₃-NdCl₃-UO₂Cl₂; POCl₂-MCl_n-NdCl₃-UO₂Cl₂ for development and synthesis of direct nuclear reaction-excited lasers. Luminescence data presented in the work were used to calculate the luminescence parameters of the laser liquids such as oscillator strengths f, probability of spontaneous radiation A, intermultiplet luminescence branching coefficient β, cross-section for induced radiation σ, luminescence decay time τ, quantum yield η, and others. It is shown that the oscillator strengths of the normal absorption bands of Na³⁺, which play the main part in the pumping processes, exceed the oscillator strengths of Na³⁺ for aqueous and many other nonaqueous systems. In the luminescence excitation spectra of the Na³⁺ ion, bands are isolated in the range 400–1000 nm atλ _rec =1.06 μm. With excitation, luminescence occurs through the⁴F_3/2→⁴I_{9/2,11/2.13/2} channels. Luminescence spectral data are related to the lasing parameters. The threshold lasing energy is∼18 J/cm³. For a resonator with mirros h₁=100% and h₂=20, 40, 56, and 80%, the lasing energy is∼20–120 MJ/cm³ in the pumping energy range 18–180 J/cm³. The differential efficiency is ∼0.2% The substantial angular radiation divergence (θ∼4·10⁻² rad) and strong thermostatic distortions that occur in the active element (dn/dT≈−1.9·10⁻⁴K⁻¹) are a disadvantage of laser liquids. It is shown that operation of neodymium- and uranium-activated inorganic liquid lasers is stable under the present conditions. A. I. Gertsen Russian State Pedagogical University, Moika Embankment, 48, St. Petersburg, 191186, Russia. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 5, pp. 607–619, September–October, 1997.     

Study of the plasmas produced during the deposition of TiC/SiC thin films in a hybrid magnetron-laser system

Time- and spatially-resolved optical emission spectroscopy was performed to characterize the plasma produced in a hybrid magnetron-sputtering-laser deposition system, which is used for TiC or SiC thin films preparation. A graphite target was ablated by a KrF excimer laser (λ=248 nm,τ=20 ns) and either Ti or Si targets were used for DC magnetron sputtering in argon ambient. Spectra were measured in the range 250–850 nm. The evolution of the spectra with varying magnetron powers (0–100 W) and argon pressures (0.3–10 Pa) was studied. Spectra of the plasmas produced by a) the magnetron alone, b) the ablation laser alone, and c) the magnetron and the ablation laser together, were recorded. Spectra (a) were dominated by Ar atoms and Ar⁺ ions. Emission lines of Ti and Si were detected, when Ti target and Si target was used, respectively. Spectra (b) revealed emission of C, C⁺, C₂, Ar, Ar⁺. Spectra (c) showed presence of all previously mentioned species and further of Ti⁺ ions emission was detected. The research was supported by Grant Agency of the Czech Republic No. 202/06/02161, GA ASCR project number A1010110/01 and Institutional Research Plan AV CR No. AV0Z 10100522.     

Parametric oscillation of high-power 3-THz pulse by synchronously pumped ZnGeP<Subscript>2</Subscript> crystal: Computer simulation

Possible parametric oscillation of 3-THz pulse at synchronous pumping of the ZnGeP₂ crystal by a train of short second-harmonic pulses from the CO₂ laser has been analyzed. Calculation shows that at changing laser pulse duration τ between 4 and 500 ps and correspondingly pumping energy density (0.5–3.5 J cm⁻²) THz pulse peak power varies from 3 to 70MW with maximum at τ =9 ps.     

Spectral-luminescent properties of condensation products of 8-aminoquinoline,aromatic aldehydes,and dimedone

Hydrobenzophenanthrolinone derivatives were synthesized by three-component condensation of 8-aminoquinoline, aromatic aldehydes, and dimedone. The structures of the obtained substances were confirmed by NMR and IR spectroscopy and mass spectrometry. Spectral-luminescent investigations of the synthesized compounds showed that they were characterized by high oscillator strengths for allowed electronic transitions S _n ← S ₀ (n = 1–3). Low fluorescence quantum yields in EtOH (Φ_fl ~ 10^–4–10^–3) and an increase of the Φfl values in toluene (~10^–2) at room temperature and with lowering the temperature to 77 K (Φ_fl ~ 10^–1) for a number of the compounds under study were satisfactorily explained within the framework of Marcus theory.     

Wet bone ablation with mechanically Q-switched high-repetition-rate CO2 laser

2 laser using a miniature water spray is demonstrated. An ablation threshold of 1.4 J/cm², an optimal energy density of 9–10 J/cm², and a corresponding specific ablation energy of 25–30 J/mm³ are found for pig thighbone compacta at λ=9.57 μm and a beam waist diameter of 0.5 mm. The water spray alleviates tissue carbonization even at high laser pulse repetition rates and increases ablation efficiency. Received: 9 March 1998/Revised version: 6 July 1998