Plasma plume induced during laser ablation of graphite

The plasma plume induced during ArF laser ablation of a graphite target is studied. Velocities of the plasma expansion front are determined by the optical time of flight method. Mass center velocities of the emitting atoms and ions are constant and amount to 1.7×10⁴ and 3.8×10⁴ m s⁻¹, respectively. Higher velocities of ions result probably from their acceleration in electrostatic field created by electron emission prior to ion emission. The emission spectroscopy of the plasma plume is used to determine the electron densities and temperatures at various distances from the target. The electron density is determined from the Stark broadening of the Ca II and Ca I lines. It reaches a maximum of ∼9.5×10²³ m⁻³ 30 ns from the beginning of the laser pulse at the distance of 1.2 mm from the target and next decreases to ∼1.2×10²² m⁻³ at the distance of 7.6 mm from the target. The electron temperature is determined from the ratio of intensities of ionic and atomic lines. Close to the target the electron temperature of ∼30 kK is found but it decreases quickly to 11.5 kK 4 mm from the target.     

PLD synthesis of GaN nanowires and nanodots on patterned catalyst surface for field emission study

Patterned gallium nitride nanowires and nanodots have been grown on n-Si (100) substrates by pulsed laser deposition. The nanostructures are patterned using a physical mask, resulting in regions of nanowire growth of different densities. The field emission (FE) characteristics of the patterned gallium nitride nanowires show a turn-on field of 9.06 V/μm to achieve a current density of 0.01 mA/cm² and an enhanced field emission current density as high as 0.156 mA/cm² at an applied field of 11 V/μm. Comparing the peak FE current densities of both the nanowires and nanodots, the peak FE current density of nanowires is around 700 times higher than that of the peak FE current density of nanodots since nanodots have a lower aspect ratio compared to nanowires. The field emission results indicate that, besides density difference, crystalline quality as well as the low electron affinity of gallium nitride, high aspect ratio of gallium nitride nanostructures will greatly enhance their field emission properties.     

High repetition rate femtosecond laser nano-machining of thin films

Thin film laser micromachining has been utilized for repairing semiconductor masks, creating solar cells and fabricating MEMS devices. A unique high repetition rate femtosecond fiber laser system capable of variable repetition rates from 200 KHz to 25 MHz along with helium gas assist was used to study the effect of pulse repetition rate and pulse energy on femtosecond laser machining of gold-coated silicon wafer. It was seen that high repetition rates lead to smaller craters with uniform line width. Craters created at 13 MHz pulse repetition rate with 2.042 J/cm² beam energy fluence measured 110 nm in width and had a heat affected zone of 0.79 μm. It was found that pulse repetition rate only played a significant role in the size of the heat affected zone in the lower pulse energy ranges. In the future, a 1 W laser system will be acquired to find the optimal repetition rate that would create the minimal feature size with the least heat affected zone. Using this kind of setup along with techniques such as radial polarization and a different gas assist may enable us to create sub 100 nm feature size with good quality.     

Fabrication of fluorescent nanoparticles of dendronized perylenediimide by laser ablation in water

Highly fluorescent organic nanoparticles with size of about 300 nm were prepared by nanosecond laser ablation of micrometer-sized powder of dendronized perylenediimide dispersed in water. The nanoparticle colloidal solution provided a fluorescence quantum yield of 0.58. The absorption and emission spectral studies demonstrated that the bulky dendron groups at the side bays of perylenediimide chromophore efficiently suppress the interchromophoric interactions in the nanoparticles. Fluorescence measurement on several single nanoparticles underlines that the prepared nanoparticles are bright and photo-stable enough to be a useful probe for single particle fluorescence investigation.     

Molecular imaging by Mid-IR laser ablation mass spectrometry

Mid-IR laser ablation at atmospheric pressure (AP) produces a mixture of ions, neutrals, clusters, and particles with a size distribution extending into the nanoparticle range. Using external electric fields the ions can be extracted and sampled by a mass spectrometer. In AP infrared (IR) matrix-assisted laser desorption ionization (MALDI) experiments, the plume was shown to contain an appreciable proportion of ionic components that reflected the composition of the ablated target and enabled mass spectrometric analysis. The detected ion intensities rapidly declined with increasing distance of sampling from the ablated surface to ∼4 mm. This was rationalized in terms of ion recombination and the stopping of the plume expansion by the background gas. In laser ablation electrospray ionization (LAESI) experiments, the ablation plume was intercepted by an electrospray. The neutral particles in the plume were ionized by the charged droplets in the spray and enabled the detection of large molecules (up to 66 kDa). Maximum ion production in LAESI was observed at large (∼15 mm) spray axis to ablated surface distance indicating a radically different ion formation mechanism compared to AP IR-MALDI. The feasibility of molecular imaging by both AP IR-MALDI and LAESI was demonstrated on targets with mock patterns. Presented at the 9-th International Conference on Laser Ablation, 2007 Tenerife, Canary Islands, Spain     

Substrate dependence of ion motion in femtosecond laser ablation cloud observed by planar laser-induced fluorescence

We have observed the motion of Sm⁺ ions as well as Sm atoms produced by femtosecond laser ablation of a solidified samarium solution sample on substrates by using a planar laser-induced fluorescence method. Kinetic energies of both Sm⁺ ions and Sm atoms increase as the electrical conductivity of the substrate decreases, which suggests the effect of surface charging. The kinetic energy of Sm⁺ ions is larger than that of Sm atoms for a variety of substrates due to the further electrical acceleration by the surface charge. The knowledge of ion motion will be the key information for the optimization of femtosecond laser simultaneous atomization and ionization of organic and inorganic samples on substrates.     

Analysis of the laser ablation processes for thin-film silicon solar cells

A detailed analysis of the monolithical series connection of thin-film silicon modules with ZnO/Ag back contact is presented. In this study, pulsed lasers with wavelengths of 1064 nm and 532 nm were used. The influence of various laser parameters like laser power, pulse overlap, etc., on the different patterning steps is discussed. The focus of this study was on the back contact patterning process. Here (i) the flake formation process during the ablation and (ii) the influence of a NIR-laser source as an alternative approach to the green laser were investigated in detail. The latter would reduce system costs if only one NIR-laser source could be used for all patterning steps.     

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.     

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.     

Morphology studies of the metal surfaces with enhanced absorption fabricated using interferometric femtosecond ablation

Recently, the enhancing of bulk metals optical absorption with focused femtosecond pulses was demonstrated. This absorption enhancement is caused by different nano- and micro-structures which are formed during laser ablation with ultrashort pulses. In this paper we study the evolution of the surface structures using interferometric ablation and compare it to normal fs-ablation. Previously we have shown that interferometric femtosecond ablation is an efficient method to fabricate absorbing metal surfaces. In this study we ablated large areas of hole-array structures with different pulse numbers in polished stainless steel and copper samples. The evolution of surface morphology and the depth of the holes for these structured surfaces are presented. In addition, the reflectance of laser generated surface structures are measured at the wavelength range of 200–2300 nm using a standard spectrophotometer.     

Laser ablation of energetic polymer solutions: effect of viscosity and fluence on the splashing behavior

Laser plasma thrusters are a new kind of propulsion system for small satellites, and work with the thrust created by the laser ablation of a target. Liquid polymer solutions are very promising fuels for such systems, provided that no splashing of the target occurs, because ejection of droplets strongly decreases the performances of the system. We have investigated the nanosecond infrared laser ablation of glycidyl azide polymer solutions containing carbon nanoparticles as absorber. Shadowgraphy imaging revealed two cases, namely splashing regime and solid-like behavior. The transition between both regimes depends on the viscosity of the solution and on the laser fluence, and is explained by the recoil force acting on the target. Appropriate conditions to avoid splashing were identified, showing that this liquid polymer solution is a suitable fuel for laser plasma thrusters.     

Scanning the laser beam for ultrafast pulse laser cleaning of paint

Aligned arrays of N₂-encapsulated multilevel branched carbon nanotubes were synthesized using a simple one step CVD method by pyrolysis of ferrocene and acetonitrile. Electron energy loss spectroscopy (EELS) and elemental mapping studies reveal that gaseous nitrogen was encapsulated in the carbon nanotubes. Batch-type pyrolysis of catalysts induced flow fluctuation of the reaction gases, resulting in the growth of branched junctions. Molecular nitrogen extruded rapidly along conical catalyst particles inducing N₂ encapsulation inside the branched nanotubes. PACS 07.78.+s; 61.46.+w; 81.07.De; 81.15.Gh     

Interference effects in 157 nm laser ablated cones in polycarbonate and application to spatial coherence measurement

Conical structures formed in 157 nm laser-ablated polycarbonate exhibit a well-defined fringe structure with a period of a few 100 nm surrounding the cone base. Experiments and modelling studies of the interference produced by these micro-conical mirrors are shown to provide a means of measuring the spatial coherence of the highly multi-mode 157 nm laser.     

Microplasma generated at solid–solid interface and its application to nanostructure formation

The dynamics of the microplasmas created at a transparent solid–solid interface were investigated extensively. Microplasmas were generated at an interface between a carbon (C) or a germanium (Ge) target and a SiO₂ substrate by irradiating a KrF excimer laser beam onto the target, and the dynamics of the plasmas were investigated with the aid of optical emission spectroscopy. Although the emission spectra that contained the characteristic emission lines and the absorption bands originated from C and Ge species were observed from the C and Ge plasmas without the SiO₂ substrate, identical spectra were obtained from both the plasmas created at the C–SiO₂ and Ge–SiO₂ interfaces. Furthermore, the target and the Si substrate surfaces were examined with a scanning electron microscope. The SiO₂ substrate was smoothly etched and a nanostructure of a chain-like morphology was also observed in the deposits on the SiO₂ substrate.     

Study of laser fragmentation process of silver nanoparticles in aqueous media

Laser fragmentation of Ag nanoparticles in Ag hydrosol was studied by simultaneous measurements of the transmitted fluence of the incident laser beam and the time evolution of the surface plasmon extinction (SPE) spectra. The experiments showed that the laser fragmentation in a small volume of hydrosol proceeds during first 20 pulses and then reaches saturation. The value of the transmitted fluence corresponding to saturation increases with incident pulse fluence, but the impact of the first pulse applied to the hydrosols shows an optical limitation. Fluences above 303 mJ/cm² cause the formation of less stable, aggregating nanoparticles, while fluences below 90 mJ/cm² do not provide sufficient energy for efficient fragmentation. The interval of fluences between 90–303 mJ/cm² is optimal for fragmentation, since stable hydrosols constituted by small, non-aggregated nanoparticles are formed.     

Formation of highly organised,periodic microstructures on steel surfaces upon pulsed laser irradiation

We present results on the growth of highly organised, reproducible, periodic microstructure arrays on a stainless steel substrate using multi-pulsed Nd:YAG (wavelength of 1064 nm, pulse duration of 7 ns, repetition rate of 25 kHz, beam quality factor of M ²∼1.5) laser irradiation in standard atmospheric environment (room temperature and normal pressure) with laser spot diameter of the target being ∼50 μm. The target surface was irradiated at laser fluence of ∼2.2 J/cm² and intensity of ∼0.31×10⁹ W/cm², resulting in the controllable generation of arrays of microstructures with average periods ranging from ∼30 to ∼70 μm, depending on the hatching overlap between the consecutive scans. The received tips of the structures were either below or at the level of the original substrate surface, depending on the experimental conditions. The peculiarity of our work is on the utilised approach for scanning the laser beam over the surface. A possible mechanism for the formation of the structures is proposed.     

Nanosecond pulsed laser ablation of silicon in liquids

Laser fluence and laser shot number are important parameters for pulse laser based micromachining of silicon in liquids. This paper presents laser-induced ablation of silicon in liquids of the dimethyl sulfoxide (DMSO) and the water at different applied laser fluence levels and laser shot numbers. The experimental results are conducted using 15 ns pulsed laser irradiation at 532 nm. The silicon surface morphology of the irradiated spots has an appearance as one can see in porous formation. The surface morphology exhibits a large number of cavities which indicates as bubble nucleation sites. The observed surface morphology shows that the explosive melt expulsion could be a dominant process for the laser ablation of silicon in liquids using nanosecond pulsed laser irradiation at 532 nm. Silicon surface’s ablated diameter growth was measured at different applied laser fluences and shot numbers in both liquid interfaces. A theoretical analysis suggested investigating silicon surface etching in liquid by intense multiple nanosecond laser pulses. It has been assumed that the nanosecond pulsed laser-induced silicon surface modification is due to the process of explosive melt expulsion under the action of the confined plasma-induced pressure or shock wave trapped between the silicon target and the overlying liquid. This analysis allows us to determine the effective lateral interaction zone of ablated solid target related to nanosecond pulsed laser illumination. The theoretical analysis is found in excellent agreement with the experimental measurements of silicon ablated diameter growth in the DMSO and the water interfaces. Multiple-shot laser ablation threshold of silicon is determined. Pulsed energy accumulation model is used to obtain the single-shot ablation threshold of silicon. The smaller ablation threshold value is found in the DMSO, and the incubation effect is also found to be absent.     

Ion extraction from the surface ablated materials in electric fields using an intense femtosecond laser pulse

In order to develop a femtosecond laser ablation (fsLA) ion source for TOF mass spectrometry, we have analyzed time-resolved images of laser-induced fluorescence from Sm⁺ ions produced by fsLA of a solid samarium in electric fields. The polarity and the strength of electric fields had a remarkable effect on the expansion of Sm⁺ ions. Moreover, accelerating electric fields elongated the duration of the ion emission from the samarium surface in fsLA, which degraded time-focusing of the ions. We have found that suppression the continuous ion emission caused by fsLA in electric fields is most important in TOF measurements.     

KF-doped BaTi<Subscript>2</Subscript>O<Subscript>5</Subscript> ferroelectric ceramics by solid-state reaction of KF and sol–gel-derived BaTi<Subscript>2</Subscript>O<Subscript>5</Subscript> powders

We report KF-doping work on the recently found ferroelectric material BaTi₂O₅. The ceramic samples, Ba_1-xK_xTi₂O_5-xF_x, were synthesized by solid-state reaction of mixed KF and sol–gel-derived BaTi₂O₅ powders at 1150 °C. An almost pure phase was obtained for nominal composition x≤0.097, while electron probe microanalysis indicated that the real incorporated K and F contents were less than half of the nominal values. It was observed that KF-doping is beneficial in enhancing the ceramic density to some extent, which is a key issue in sol–gel-derived BaTi₂O₅ ceramics, due to a possible liquid-phase sintering mechanism through the presence of melted KF at the sintering temperature. Scanning electron microscopy images showed that these porous ceramic samples are composed of sub-micron-sized powder aggregates which, with increasing KF-doping, undergo further agglomeration. Dielectric measurement from room temperature to ∼ 560 °C showed a broad ferroelectric phase transition, with T_C ∼ 430 °C for the undoped sample. As KF-doping increases, T_C decreases, and the magnitude of the dielectric constant maximum also displays a decreasing trend. The strongly reduced dielectric response can be partly understood by regarding the porous ceramic sample as a composite material composed of bulk BaTi₂O₅ and air, where the porosity has a significant influence on the effective dielectric constant. PACS 77.84.-s; 77.84.Dy; 81.20.Fw