Pulsed laser CVD investigations of single-wall carbon nanotube growth dynamics

The nucleation and rapid growth of single-wall carbon nanotubes (SWNTs) were explored by pulsed-laser assisted chemical vapor deposition (PLA-CVD). A special high-power, Nd:YAG laser system with tunable pulse width (>0.5 ms) was implemented to rapidly heat (>3×10⁴°C/s) metal catalyst-covered substrates to different growth temperatures for very brief (sub-second) and controlled time periods as measured by in situ optical pyrometry. Utilizing growth directly on transmission electron microscopy grids, exclusively SWNTs were found to grow under rapid heating conditions, with a minimum nucleation time of >0.1 s. By measuring the length of nanotubes grown by single laser pulses, extremely fast growth rates (up to 100 microns/s) were found to result from the rapid heating and cooling induced by the laser treatment. Subsequent laser pulses were found not to incrementally continue the growth of these nanotubes, but instead activate previously inactive catalyst nanoparticles to grow new nanotubes. Localized growth of nanotubes with variable density was demonstrated through this process and was applied for the reliable direct-write synthesis of SWNTs onto pre-patterned, catalyst-covered metal electrodes for the synthesis of SWNT field-effect transistors.     

Femtosecond laser ablation characteristics of nickel-based superalloy C263

Femtosecond laser (180 fs, 775 nm, 1 kHz) ablation characteristics of the nickel-based superalloy C263 are investigated. The single pulse ablation threshold is measured to be 0.26±0.03 J/cm² and the incubation parameter ξ=0.72±0.03 by also measuring the dependence of ablation threshold on the number of laser pulses. The ablation rate exhibits two logarithmic dependencies on fluence corresponding to ablation determined by the optical penetration depth at fluences below ∼5 J/cm² (for single pulse) and by the electron thermal diffusion length above that fluence. The central surface morphology of ablated craters (dimples) with laser fluence and number of laser pulses shows the development of several kinds of periodic structures (ripples) with different periodicities as well as the formation of resolidified material and holes at the centre of the ablated crater at high fluences. The debris produced during ablation consists of crystalline C263 oxidized nanoparticles with diameters of ∼2–20 nm (for F=9.6 J/cm²). The mechanisms involved in femtosecond laser microprocessing of the superalloy C263 as well as in the synthesis of C263 nanoparticles are elucidated and discussed in terms of the properties of the material.     

Ablation and analysis of small cell populations and single cells by consecutive laser pulses

Laser ablation of single cells through a sharpened optical fiber is used for the detection of metabolites by laser ablation electrospray ionization (LAESI) mass spectrometry (MS). Ablation of the same Allium cepa epidermal cell by consecutive pulses indicates the rupture of the cell wall by the second shot. Intracellular sucrose heterogeneity is detected by subsequent laser pulses pointing to rupturing the vacuolar membrane by the third exposure. Ion production by bursts of laser pulses shows that the drying of ruptured A. cepa cells occurs in ∼50 s at low pulse rates (10 pulses/s bursts) and significantly faster at high pulse rates (100 pulses/s bursts). These results point to the competing role of cytoplasm ejection and evaporative drying in diminishing the LAESI-MS signal in ∼50 s or 100 laser pulses, whichever occurs first.     

Growth of single-wall carbon nanotubes dependent on laser power density and ambient gas pressure during room-temperature CO2 laser vaporization

Single-wall carbon nanotubes (SWNTs) were synthesized by the irradiation of 20-ms CO₂ laser pulses onto a graphite–Co/Ni target at room temperature. We investigated the effect of laser power density (10–150 kW/cm²) and ambient Ar gas pressure (150–760 Torr) on the abundance of SWNTs with lengths of up to about 200 nm in soot-like carbonaceous deposits. For a constant power density (30 kW/cm²), depending on the Ar gas pressure, SWNTs with diameters of 1.2–1.4 nm were synthesized. Expansion behavior and temperature-fall rates of clusters and/or particles in laser plumes were also analyzed by high-speed video imaging and temporally and spatially resolved emission spectroscopy. The temperature-fall rates were estimated to be 171–427 K/ms. The SWNT growth on the time scale of a few milliseconds appeared to be related to some features of condensing clusters and/or particles, including resident densities, collision frequencies and temperatures. Received: 16 July 2001 / Accepted: 23 July 2001 / Published online: 30 August 2001     

Mechanisms of ablation-rate decrease in multiple-pulse laser ablation

We present two sets of experimental results on the ablation-rate decrease with increase of the number of consecutive laser pulses hitting the same spot on the target surface. We have studied laser ablation of a carbon target with nanosecond pulses in two different interaction regimes: one with a XeCl laser (λ=308 nm) and the other with a Nd:YAG laser (λ=1064 nm), in both cases at the intensity ∼5×10⁸ W/cm² Two different mechanisms were found to be responsible for the ablation-rate decrease; they are directly related to the two different laser–matter interaction regimes. The UV-laser interaction is in the regime of transparent vapour (surface absorption). The increase of the neutral vapour density in the crater produced by the preceding laser pulses is the main reason for the decrease of ablation rate. With the IR laser each single laser pulse interacts with a partially ionised plume. With increase of the number of pulses hitting the same spot on the target surface, the laser–matter interaction regime gradually changes from the near-surface absorption to the volume absorption, resulting in the decrease in absorption in the target and thus in the decrease in the ablation rate. The change in the evaporation rate was considered for both vacuum and reactive-gas environments. Received: 21 February 2001 / Accepted: 26 February 2001 / Published online: 23 May 2001     

Laser-assisted generation of self-assembled microstructures on stainless steel

Utilising a Nd:YVO₄ laser (wavelength of 532 nm, pulse duration of 8 ns, repetition rate of 30 kHz) and a Nd:YAG laser (wavelength of 1064 nm, pulse duration of 7 ns, repetition rate of 25 kHz), it was found that during the pulsed laser ablation of metal targets, such as stainless steel, periodic nodular microstructures (microcones) with average periods ranging from ∼30 to ∼50 μm were formed. This period depends on the number of accumulated laser pulses and is independent of the laser wavelength. It was found that the formation of microcones could occur after as little as 1500 pulses/spot (a lower number than previously reported) are fired onto a target surface location at laser fluence of ∼12 J/cm², intensity of ∼1.5 GW/cm². The initial feedback mechanism required for the formation of structures is attributed to the hydrodynamic instabilities of the melt. In addition to this, it has been shown that the structures grow along the optical axis of the incoming laser radiation. We demonstrate that highly regular structures can be produced at various angles, something not satisfactorily presented on metallic surfaces previously. The affecting factors such as incident angle of the laser beam and the structures that can be formed when varying the manner in which the laser beam is scanned over the target surface have also been investigated.     

Microdrilling of metals with an inexpensive and compact ultra-short-pulse fiber amplified microchip laser

We have investigated the ultra-fast microdrilling of metals using a compact and cheap fiber amplified passively Q-switched microchip laser. This laser system delivers 100-ps pulses with repetition rates higher than 100 kHz and pulse energies up to 80 μJ. The ablation process has been studied on metals with quite different thermal properties (copper, carbon steel and stainless steel). The dependence of the ablation depth per pulse on the pulse energy follows the same logarithmic scaling laws governing laser ablation with sub-picosecond pulses. Structures ablated with 100-ps laser pulses are accompanied only by a thin layer of melted material. Despite this, results with a high level of precision are obtained when using the laser trepanning technique. This simple and affordable laser system could be a valid alternative to nanosecond laser sources for micromachining applications.     

Impact of the lasr wavelength and fluence on the ablation rate of aluminium

The dependence of the ablation rate of aluminium on the fluence of nanosecond laser pulses with wavelengths of 532 nm and respectively 1064 nm is investigated in atmospheric air. The fluence of the pulses is varied by changing the diameter of the irradiated area at the target surface, and the wavelength is varied by using the fundamental and the second harmonic of a Q-switched Nd-YAG laser system. The results indicate an approximately logarithmic increase of the ablation rate with the fluence for ablation rates smaller than ∼6 μm/pulse at 532 nm, and 0.3 μm/pulse at 1064 nm wavelength. The significantly smaller ablation rate at 1064 nm is due to the small optical absorptivity, the strong oxidation of the aluminium target, and to the strong attenuation of the pulses into the plasma plume at this wavelength. A jump of the ablation rate is observed at the fluence threshold value, which is ∼50 J/cm² for the second harmonic, and ∼15 J/cm² for the fundamental pulses. Further increasing the fluence leads to a steep increase of the ablation rate at both wavelengths, the increase of the ablation rate being approximately exponential in the case of visible pulses. The jump of the ablation rate at the threshold fluence value is due to the transition from a normal vaporization regime to a phase explosion regime, and to the change of the dimensionality of the hydrodynamics of the plasma-plume.      

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.     

Control of material removal of fused silica with single pulses of few optical cycles to sub-picosecond duration

Surface ablation of a dielectric material (fused silica) by single femtosecond pulses is studied as a function of pulse duration (7–450 fs) and applied fluence (F _th<F<10F _th). We show that varying the pulse duration gives access to high selectivity (with resolution ∼10 nm) for axial removal of matter but does not influence the transverse ablation selectivity, which only depends on the normalized applied fluence F/F _th. The ablation efficiency is shown to be inversely dependent on the pulse duration and saturates with respect to the applied fluence earlier at ultra-short pulse durations (≤30 fs). The deduced optimal fluence F _opt corresponding to the highest ablation efficiency for each pulse width defines two regimes of laser application. Below F _opt, the removed material depth can be accurately adjusted in a large range (∼40–200 nm) as a function of the applied fluence and the morphology of the ablated pattern almost reproduces the Gaussian beam distribution. Above F _opt, the material removal depth tends to saturate and the morphology of the ablated pattern evolves to a top-hat distribution. The coupled evolution of depth and morphology is related to the dynamics of formation of dense plasma at the surface of the material, acting as an ultra-fast optical shutter.     

Fabrication of completely filled carbon nanotubes with copper nanowires in a confined space

Carbon nanotubes (CNTs) filled completely with polycrystalline Cu nanowires were synthesized by laser vaporization of Cu and graphite under high-pressure Ar gas atmosphere. Depending on the Ar gas pressure (0.1–0.9 MPa) and the Cu content (1–40 at.%) in graphite targets for laser vaporization, various products with different morphologies were observed by scanning and transmission electron microscopy. The ratios of the Cu-filled CNTs and carbon nanocapsules particularly increased as Ar gas pressure was increased. The maximum ∼60% fraction of Cu-filled CNTs with outer diameter of 10–50 nm and length of 0.3–3 μm was achieved at 0.9 MPa from graphite containing 20 at.% Cu. Most of the encapsulated Cu-nanowires were surrounded by single, double, or triple graphitic layers. Although the yield of the Cu-filled CNTs was also dependent on the Cu content in the graphite targets, no unfilled CNTs were produced even for low Cu content. The growth of Cu-filled CNTs is explained by the formation of molten Cu–C composite particles with an unusually C-rich composition in a space confined by high-pressure Ar gas, followed by precipitating Cu and C from the particles and subjecting them to phase separation.     

CdSe &; ZnS core/shell nanoparticles generated by laser ablation of microparticles

Laser Ablation of Microparticles (LAM) is a process of nanoparticle formation in which microparticles in a flowing aerosol are continuously ablated by high-power laser pulses. For the first time, we have produced CdSe/ZnS core/shell nanoparticles using a double ablation apparatus, designed to undergo a two-step LAM process. This process can be inverted to produce ZnS/CdSe core/shell nanoparticles. The present work focuses on the range around ∼15 nm radius heterostructures and uses high-resolution transmission electron microscopy (HRTEM) to image core and shells. For smaller particles, core shell structures have been detected with energy dispersive spectroscopy (EDS) 5 nm spot size beam and fast Fourier transform (FFT) spectra. Differences in the ablation behavior were measured between the two IIB–VIA type semiconductors.     

Long duration light emission from femtosecond laser–target interactions

Time resolved emission from the interaction of ultra-short (∼200 fs) laser pulses with aluminum and copper targets was investigated. Measurements show that emission from the laser produced plasma in air is significantly more intense than in near vacuum conditions and that the emission in air can extend for periods exceeding 100 ns. Modeling the laser–target–air coupling shows that the laser–target interaction can lead to blast wave shock waves being launched in the ambient air and that the emission from the shocked air dominates over emission from the target surface. The long term emission measurements in air are in agreement with the modeling results.     

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     

Excitation of X rays by electrons accelerated in air in the wake wave of a laser pulse

The characteristics of X rays of a laser plasma generated in the interaction of a femtosecond pulse with solid targets in an air atmosphere have been investigated. It has been shown that the mechanism for the generation of X rays in the interaction of short intense laser pulses with solid targets in a gas atmosphere is attributed to the generation of fast electrons in the region of the filamentation of a laser pulse. It has been proven experimentally that under such conditions, the solid target irradiated by laser radiation of even a low density of about 10¹⁵ W/cm² very efficiently emits ∼10-keV photons. It has been shown theoretically that the maximum energy of accelerated electrons can reach ɛ_max ∼ 100–200 keV under these conditions. This means that the proposed method can provide characteristic radiation with the energy of photons much higher than 10 keV.     

II–VI semiconductor nanoparticles synthesized by laser ablation

Nanoparticles of the II–VI semiconductors CdTe, CdSe and ZnTe were synthesized by laser ablation (387 nm, 180 fs, 1 kHz, pulse energy of 7 μJ (fluence of 2 J/cm²)) of the target materials in methanol, de-ionized water and acetone. The nanoparticles size distributions follow log-normal functions with median diameters between about 6 and 11 nm for the several materials. The nanoparticles have the same crystalline structure as that of the corresponding bulk material and under the present conditions of ablation are rich in the higher volatility element of the two in the binary alloy and oxidized. Photoluminescence emission in the green-yellow (∼570 nm) was detected from CdSe nanoparticles.     

Laser ablation and micropatterning of thin TiN coatings

Laser ablation of thin TiN films deposited on steel substrates has been studied under wide-range variation of irradiation conditions (pulsewidth, wavelength, energy density and spot size). It has been demonstrated that both picosecond (150–300 ps) and nanosecond (5–9 ns) laser pulses were suitable for controllable ablation and microstructuring of a 1-μm-thick TiN film unlike longer 150-ns pulses. The ablation rate was found to be practically independent of the wavelength (270–1078 nm) and pulsewidth (150 ps–9 ns), but it increased substantially when the size of a laser spot was reduced from 15–60 μm to 3 μm. The laser ablation technique was applied to produce microstructures in the thin TiN films consisting of microcraters with a typical size of 3–5 μm in diameter and depth less than 1 μm. Tests of lubricated sliding of the laser-structured TiN films against a steel ball showed that the durability of lubricated sliding increased by 25% as compared to that of the original TiN film. Received: 28 July 1999 / Accepted: 17 April 2000 / Published online: 20 September 2000     

Patterning of PLZT and PSZT thin films by excimer laser

The patterning of lanthanum-doped lead zirconate titanate (PLZT) and strontium-doped lead zirconate titanate (PSZT) thin films has been examined using a 5-ns pulsed excimer laser. Both types of film were deposited by rf magnetron sputtering with in situ heating and a controlled cooling rate in order to obtain the perovskite-structured films. The depth of laser ablation in both PSZT and PLZT films showed a logarithmic dependence on fluence. The ablation rate of PLZT films was slightly higher than that of PSZT films over the range of fluence (10–150 J/cm²) and increased linearly with number of pulses. The threshold fluence required to initiate ablation was ∼ 1.25 J/cm² for PLZT and ∼ 1.87 J/cm² for PSZT films. Individual squares were patterned with areas ranging from 10×10 μm² up to 30×30 μm² using single and multiple pulses. The morphology of the etched surfaces comprised globules which had diameters of 200–250 nm in PLZT and 1400 nm in PSZT films. The diameter of the globules has been shown to increase with fluence until reaching an approximately constant size at ≤ 20 J/cm² in both types of film. The composition of the films following ablation has been compared using X-ray photoelectron spectroscopy and energy-dispersive X-ray spectroscopy. PACS 79.20.Ds; 82.80.Pv; 82.80.Ej     

Short-laser-pulse-driven emission of energetic ions into a solid target from a surface layer spalled by a laser prepulse

An efficient emission of picosecond bunches of energetic protons and carbon ions from a thin layer spalled from a organic solid by a laser prepulse is demonstrated numerically. We combine the molecular dynamics technique and multi-component collisional particle-in-cell method with plasma ionization to simulate the laser spallation and ejection of a thin (∼20–30 nm) solid layer from an organic target and its further interaction with an intense femtosecond laser pulse. In spite of its small thickness, a layer produced by laser spallation efficiently absorbs ultrashort laser pulses with the generation of hot electrons that convert their energy to ion energy. The efficiency of the conversion of the laser energy to ions can be as high as 20%, and 10% to MeV ions. A transient electrostatic field created between the layer and surface of the target is up to 10 GV/cm. Received: 13 March 2001 / Accepted: 20 March 2001 / Published online: 20 June 2001     

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.