Shadowgraphic and emission imaging spectroscopic studies of the laser ablation of graphite in an Ar gas atmosphere

Laser ablation of graphite in an Ar atmosphere at 560 Torr was done using a nanosecond-pulse Nd:YAG laser (1064 nm) at a fluence of 12 J/cm². Dynamics in the ejection of carbon species and in their confinement near the graphite surface (<1 mm) due to their numerous collisions with Ar atoms were investigated by shadowgraphy, emission imaging, and emission spectroscopy at delay times of 0.01-100 7s following the laser irradiation. A shock wave was generated, and temporally and spatially dependent emissions from Ar⁺ and Ar were observed in addition to those from carbon species (C, C⁺, and C₂) and the Bremsstrahlung radiation from a hot plasma. We suggest that the dissipation of the kinetic and thermal energies of the carbon species, their backward motion, and their collisions with each other lead to the formation of clusters and particles through the interaction with Ar atoms.     

Diagnostics of laser-produced plume under carbon nanotube growth conditions

This paper presents diagnostic data obtained from the plume of a graphite composite target during carbon nanotube production by the double-pulse laser oven method. The in situ emission spectrum (300 to 650 nm) is recorded at different locations upstream of the target and at different delay times from the lasers (IR and green). Spectral features are identified as emissions from C₂ (Swan System: d³@_g-a³@_u) and C₃ (Comet Head System: A¹@_u-X¹D_u⁺). Experimental spectra are compared with computed spectra to estimate vibrational temperatures of excited state C₂ in the range of 2500 to 4000 K. The temporal evolution of the 510-nm band of C₂ is monitored for two target positions in various locations, which shows confinement of the plume in the inner tube and increase in plume velocity with temperature. The excitation spectra of C₂ are obtained by using a dye laser to pump the (0,1) transition of the Swan System and collecting the laser-induced fluorescence signal from C₂. These are used to obtain "ground-state" rotational and vibrational temperatures which are close to the oven temperature. Images of the plume are also collected and are compared with the spectral measurements.     

Nanocrystalline growth and diagnostics of TiC and TiB2 hard coatings by pulsed laser deposition

Nanocrystalline coatings of TiC and TiB₂ were grown by pulsed laser deposition on Si(100) and on X155 steel at low substrate temperatures ranging from 40 °C to 650 °C. A pulsed KrF excimer laser was used with the deposition chamber at a base pressure of 10^-6 mbar. The morphology and structure of the films, studied with SEM, XRD, and TEM, showed that nanocrystalline films with a fine morphology of TiC and TiB₂ were deposited with a grain size of 10 nm-70 nm at all substrate temperatures. The growth of the polycrystalline coatings possessed a columnar morphology with a 𘜄¢ preferred orientation. The hardness of the coatings was determined to be 40 GPa and the elastic modulus, 240 GPa. The composition and the kinetics of the plume produced during the pulsed laser deposition of TiC and TiB₂ was studied under film growth conditions. The mass analysis of ions of the ejected material was performed by time-of-flight mass spectroscopy (TOF-MS) and showed the presence of Ti⁺ and C⁺ during TiC ablation and B⁺, B₂⁺, and Ti⁺ during TiB₂ ablation. The kinetic energies (KE) of the ions depended on the laser fluence which was between 0.5 eV and 340 eV. The kinetic energy and the evolution of the plasma was studied with a streak camera. The velocity of the plasma was of the order of 10⁶ cm/sec and was linearly dependent on the energy fluence of the laser. The emission spectroscopy of the plasma plume confirmed the atomic neutral and single excited species of Ti. These results show that coating growth basically occurs by the recombination of the ionic species at the surface of the substrate.     

Fast imaging of the plume expansion produced by laser ablation of LiNbO3

Fast photography of the plume produced by laser ablation of LiNbO₃ in vacuum has been performed using an image intensified CCD (ICCD) camera in a time interval up to 2 7s after the laser pulse. Two differently oriented single crystalline LiNbO₃ targets were used. The results show that although the emission intensity of the laser-generated plume initially depends on the crystalline orientation of the target, it reaches a stationary state after several minutes which is the same for both targets orientations. Under these stationary conditions, the angular distribution of the Li atoms is found to be broader than that of Nb atoms. The observed less forward directed expansion of the Li species may explain the poor Li content normally observed in films grown by laser ablation of LiNbO₃ in vacuum.     

193-nm laser ablation of CVD diamond and graphite in vacuum: plume analysis and film properties

The pulsed laser ablation of chemical vapor deposition (CVD) diamond and graphite samples in vacuum has been investigated by the use of an ArF excimer laser operating at 5=193 nm. The composition and propagation of both ablation plumes has been probed via wavelength and spatially and temporally resolved measurements of the plume emission and found to be very similar. Electronically excited C atoms and C⁺ and C²⁺ ions are identified among the ablated material. Plume expansion velocities are estimated from time-gated imaging of specific C and C⁺ emissions. Langmuir probe measurements provide further insight into the propagation of the charged components in both ablation plumes. Diamond-like carbon (DLC) films grown by 193-nm laser ablation of both target materials on Si substrates maintained at room temperature have been investigated by laser Raman spectroscopy (325 nm and 488 nm excitation) and by both optical and scanning electron microscopy, and their field emission characteristics investigated. Again, similarities outweigh the differences, but DLC films grown from ablation of the diamond target appear to show steeper I/V dependencies once above the threshold voltage for field emission.     

A novel route to aligned nanotubes and nanofibres using laser-patterned catalytic substrates

We describe the generation of aligned carbon nanotube bundles and films by pyrolysis of solid organic precursors (for example 2-amino-4,6-dichloro-s-triazine, s-triaminotriazine) at 950-1050 °C over laser-patterned thin metal (Fe, Co, Ni) films, deposited on silica substrates. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) studies reveal that surface roughness of the laser-etched catalytic substrates plays a key role in achieving control of nanotube growth. We believe that, during the etching process, the energised (ablated) metal clusters condense and recrystallise evenly, possibly as the metal oxide, within the edges or surface of the eroded regions. During pyrolysis these catalytic particles, embedded in the silica substrates, are responsible for carbon agglomeration and subsequent tube axial growth, suggesting that nanotube alignment strongly depends upon the etching conditions (for example laser power, pulse duration, and focal distance). The pyrolysed products (usually nanotubes or nanofibres) were characterised by SEM, high-resolution transmission electron microscopy (HRTEM), electron energy loss spectroscopy (EELS) and energy dispersive X-ray spectroscopy (EDX). Samples containing only small amounts of amorphous carbon and other carbonaceous particles are notably absent. We observe that the degree of graphitisation is dependent upon the catalyst and the organic precursor. Interestingly, a nitrogen content З% was detected within the nanofibres, which exhibit corrugated graphite-like morphologies. This pyrolytic method may be used to advantage in generating aligned heteroatomic nanostructures such as B_xC_yN_z systems.     

Short-pulse laser deposition of diamond-like carbon thin films

The high intensities present in and the non-thermal nature of ultrashort-pulse laser ablation provide a nearly ideal source for thin-film deposition. The high kinetic energies and high ion content in the ablation plume suggest that it would be useful for the creation of diamond thin films. We used a 120 fs, 3 W, 1 kHz laser to ablate a graphite target and characterized the resulting films. We were able to grow amorphous films of up to 18 7m thick and free from graphite particulates with no annealing necessary and at rates up to 25 7m/hr. The films had 40-50% sp³ bonds as measured by using EELS and had properties typical of PLD-generated diamond-like carbon films.     

Diagnostics of laser-ablated carbon plumes by photoionization using a tunable laser

Tunable laser pulses at wavelengths from 250 to 880 nm were fired at plumes produced by laser ablation of a carbon target in He atmosphere. We observed an electrical current due to photoionization, which roughly reflected the behavior of carbon clusters in the plume. The photoionization current had dynamic temporal variations, comprising a rapid increase at the beginning (T_D<0.2 ms, where T_D is the time after a YAG laser pulse for laser ablation irradiates the target), a gradual increase for 0.2D<3 ms, and a slow decrease for T_D>7 ms. The increasing phase of the photoionization current was synchronized with the decreasing phase of C₂ radical density. For He gas pressures lower than 0.8 Torr no photoionization current was detected. The growth rate of the photoionization current was higher for a higher He gas pressure.     

Dual-beam ablation of fused silica by multiwavelength excitation process using KrF excimer and F2 lasers

A new technique of dual-beam laser ablation of fused silica by multiwavelength excitation process using a 248-nm KrF excimer laser (ablation beam) coupled with a 157-nm F₂ laser (excitation beam) in dry nitrogen atmosphere is reported. The dual-beam laser ablation greatly reduced debris deposition and, thus, significantly improved the ablation quality compared with single-beam ablation of the KrF laser. High-quality ablation can be achieved at the delay times of KrF excimer laser irradiation shorter than 10 ns due to a large excited-state absorption. The ablation rate can reach up to 80 nm/pulse at the fluence of 4.0 J/cm² for the 248-nm laser and 60 mJ/cm² for the F₂ laser. The ablation threshold and effective absorption coefficient of KrF excimer laser are estimated to be 1.4 J/cm² and 1.2᎒⁵ cm^-1, respectively.     

The production of sub-micron sodium nitrate particles by laser ablation

Laser ablation is a useful source of particles for chemical analysis by inductively coupled mass spectroscopy in many applications. Optimum particle transport and ionization requires particles with sizes in the range 0.1-2 7m. Significant questions remain as to the mechanisms behind particle production by laser ablation. In this work, we collect and observe particles produced from single-crystal sodium nitrate during irradiation at 1.06 7m as a function of fluence and explore the possibility that laser-induced fracture may produce suitable particles. At fluences between 3 and 4 J/cm², single laser pulses incident on cleaved samples produce large numbers of fracture particles as a result of the fracture of undercut cleavage steps. Polished samples, lacking cleavage steps, yield few, if any, particles. As the fluence is raised to 5 J/cm², a small breakdown plume is observed and large melted droplets (~10 7m in diameter) are produced from both cleaved and polished targets, presumably by spallation of a thick melted layer. Particle generation by fracture has the potential to produce particles whose composition closely matches the local sample composition.     

Continuous-wave laser properties of 4F3/2?4I13/2 channel in the Nd3+LiNbO3:ZnO non-linear crystal

This work reports for the first time continuous-wave laser action at room temperature around 1.3 7m in Nd³⁺ doped LiNbO₃:ZnO. Optical spectroscopy has been used to determine the main laser characteristics of ⁴F_3/2‘⁴I_13/2 channel, such as emission cross section and excited-state absorption cross section at laser wavelengths. Internal optical losses have been estimated from laser gain experiments. Under non-optimal conditions laser slope efficiencies of 30% have been obtained.     

Subpicosecond laser ablation of copper and fused silica: Initiation threshold and plasma expansion

We investigated the subpicosecond laser ablation of copper and fused silica under 100 fs laser irradiation at 800 nm in vacuum by means of fast plume imaging and time- and space-resolved optical emission spectroscopy. We found that, to the difference of copper ablation, the laser-generated plasma from a fused silica target exhibited one “main” component only. The “slow” plasma component, observed during copper ablation and usually assigned to optical emission from nanoparticles was not detected by either plasma fast imaging or optical emission spectroscopy even when fused silica targets were submitted to the highest incident fluences used in our experiments. The characteristic expansion velocity of this unique component was about three times larger than the velocity of the fast plume component observed during copper ablation. The dependence of laser fluence on both plasma expansion and ablation rate was investigated and discussed in terms of ablation efficiency and initiation mechanisms.     

Highly reproducible large-area and double-sided pulsed laser deposition of HTSC YBCO:Ag thin films for microwave applications

Large-area pulsed laser deposition (PLD) producing high-quality YBa₂Cu₃O_7-x (YBCO) thin films on both sides of R-plane sapphire substrates with CeO₂ buffer layer is used routinely to optimize planar microwave stripline filters for satellite and mobile communication systems. A relatively simple PLD arrangement with fixed laser plume and rotating substrate, with an offset between the laser plume and the center of the substrate is employed to deposit laterally homogeneous 3-inch-diameter Ag-doped YBCO thin films. The YBCO:Ag films are about 250 nm thick and have laterally homogeneous critical current densities of more than 3.5 MA/cm² at 77 K and homogeneous maps of microwave surface resistance R_s of about 40 m Q at 145 GHz and 77 K. The R_s at 8.5 GHz and 77 K, determined in the center position of the YBCO:Ag films, remains constant at about 370 7 Q up to a microwave surface magnetic field of about 10 mT. After experience with more than 700 double-sided 3-inch-diameter films, a high degree of homogeneity and reproducibility of j_c and R_s is reached. The PLD-YBCO:Ag films are suitable for microwave applications envisaged for future communication systems.     

Growth of oriented Pb(ZrxTi1-x)O3 thin films on glass substrates by pulsed laser deposition

Oriented crystalline Pb(Zr_xTi_1-x)O₃ (x=0.53) (PZT) thin films were deposited on metallized glass substrates by pulsed laser deposition (1060-nm wavelength Nd:YAG laser light, 10-ns pulse duration, 10-Hz repetition rate, 0.35-J/pulse and 25-J/cm² laser fluence), from a commercial target at substrate temperatures in the range 380-400 °C. Thin films of 1-3 7m were grown on Au(111)/ Pt/NiCr/glass substrates with a rate of about 1 Å/pulse on an area of 1 cm². The deposited PZT films with perovskite structure were oriented along the (111) direction, as was revealed from X-ray diffraction spectra. Fourier transform infrared spectroscopy (FTIR) was performed on different PZT films so that their vibrational modes could be determined. Piezoelectric d₃₃ coefficients up to 30 pC/N were obtained on as-deposited films. Ferroelectric hysteresis loops at 100 Hz revealed a remanent polarization of 20 7C/cm² and a coercive field of 100 kV/cm.     

Pulsed laser deposition of carbon nitride films by a sub-ps laser

CN_x (0.01-2 to 0.6 mbar the nitrogen content of the films increases monotonously, as determined by X-ray photoelectron spectroscopy. Raman spectroscopy reveals that the films consist predominantly of highly amorphous carbon.     

Investigation of plumes produced by material ablation with two time-delayed femtosecond laser pulses

We experimentally investigated and herewith reported the results of laser ablation of copper and gold with two time-delayed femtosecond laser pulses at 800 nm in vacuum. The ablation plume dynamic was monitored by fast plume imaging and time- and space-resolved optical emission spectroscopy. Optical microscopy was used to follow the ablation depth as a function of the delay between the two laser pulses. Nanoparticles deposition on mica substrates was analysed by atomic force microscopy.We estimate roughly the plume's atomization degree - that is the mass fraction of atomized material over the total ablated mass - from the relative intensities of radiation emitted from atoms and nanoparticles. It is shown that the atomization degree depends critically on the time delay between both laser pulses and on the characteristic time of electron-lattice relaxation. The increase of the atomization degree is accompanied by the decrease of the ablation depth. Atomic force microscopy measurements confirm the partial atomization of nanoparticles, as the analyses of particle deposition on mica substrates show a large decrease of the number of nanoparticles for large delay between the two pulses.     

Growth dynamics of carbon-metal particles and nanotubes synthesized by CO2 laser vaporization

To study the growth of carbon-Co/Ni particles and single-wall carbon nanotubes (SWNTs) by 20 ms CO₂ laser-pulse irradiation of a graphite-Co/Ni (1.2 at. %) target in an Ar gas atmosphere (600 Torr), we used emission imaging spectroscopy and shadowgraphy with a temporal resolution of 1.67 ms. Wavelength-selected emission images showed that C₂ emission was strong in the region close to the target (within 2 cm), while for the same region the blackbody radiation from the large clusters or particles increased with increasing distance from the target. Shadowgraph images showed that the viscous flow of carbon and metal species formed a mushroom or a turbulent cloud spreading slowly into the Ar atmosphere, indicating that particles and SWNTs continued to grow as the ejected material cooled. In addition, emission imaging spectroscopy at 1200 °C showed that C₂ and hot clusters and particles with higher emission intensities were distributed over much wider areas. We discuss the growth dynamics of the particles and SWNTs through the interaction of the ambient Ar with the carbon and metal species released from the target by the laser pulse.     

Imaging-XPS/Raman investigation on the carbonization of polyimide after irradiation at 308 nm

The laser ablation of polyimide was studied using 308 nm laser irradiation 𙜡 mJ cm^-2. Confocal Raman microscopy revealed the deposition of carbon surrounding the ablation crater, which consists of amorphous carbon with some crystalline features. Inside the crater, graphitic material was detected on top of the cones, very similar to the material from cw-Ar⁺ ion laser irradiation. FT-Raman measurements reveal the presence of intermediates of the polyimide decomposition. Imaging-X-ray photoelectron spectroscopy confirmed the deposition of carbon material surrounding the ablation crater and showed that the oxygen and nitrogen contents of the remaining material decrease.     

Formation process of Si nanoparticles in rare gas observed by a decomposition method

We have investigated the formation process of silicon nanoparticles after laser ablation of silicon targets in argon gas. The nanoparticles exhibit bright photoluminescence in the visible wavelength range and can be applied to opto-electronic devices. In order to observe silicon nanoparticles, we have developed a decomposition method. The nanoparticles were probed by detecting light emission resulting from decomposition using a second laser. This method enables us to observe nanoparticles that cannot be observed directly by the methods applied so far. We have observed that the nanoparticles grow in time periods of 1.0-1.8 ms following ablation in Ar gas at 5 Torr when Si targets are ablated at 5 J/cm² with a pulse width of 7 ns. The nanoparticles begin to grow above ablation spots slightly apart from the targets just after thermalization of the plume. We also found that the growth is delayed at higher fluxes of ablation laser light.