An Effective Method of Producing Small Neutral Carbon Clusters

An effective method of producing small neutral carbon dusters Cn （n = 1-6） is described. The small carbon dusters （positive or negative charge or neutral） are formed by plasma which are produced by a high power 532nm pulse laser ablating the surface of the metal Mn rod to react with small hydrocarbons supplied by a pulse valve, then the neutral carbon clusters are extracted and photo-ionized by another laser （266nm or 355nm） in the ionization region of a linear time-of-flight mass spectrometer. The distributions of the initial neutral carbon dusters are analysed with the ionic species appeared in mass spectra. It is observed that the yield of small carbon dusters with the present method is about 10 times than that of the traditional widely used technology of laser vaporization of graphite.     

Mass spectrometric studies of laser ablated plume from a superconducting material

The ionic species present in the laser ablated plume from the surface of the Bi_1.6Pb_0.4Sr₂Ca₂Cu₃O_ysuperconducting target have been investigated using a non-commercial laboratory developed linear time-of-flight (TOF) mass spectrometer. The recorded TOF mass spectra reveal the presence of all the atomic species of the target material, monoxide and cluster ions. The occurrence of clusters in the mass spectra is the evidence of aggregation processes at higher laser fluence. The dependence of the ionic yield of the species has been studied using the fundamental (1064 nm), second harmonic (532 nm) and fourth harmonic (266 nm) of a Nd:YAG laser. The maximum ionization of the species present in the plume is observed at 266 nm even at lower laser fluence. The effect of the laser fluence on the total and individual ionic yields of the ablated species is also presented.     

Silicon cluster formation in the laser ablation of SiO at 308 nm

Neutral silicon cluster formation in the laser (308 nm) ablation of silicon monoxide was investigated through the analysis of composition and dynamics of the ablation plume under different laser fluence conditions. The neutral species were ionized by a second laser (193 nm) and the positionized species detected by TOF-MS (time-of-flight mass spectrometry). At low laser fluences, plume composition is dominated by SiO; above 0.6 J/cm² Si, SiO and Si₂ have comparable intensity and Si_n (n≤7) clusters are observed. Flow velocities and temperatures of the ejected species are nearly mass-independent, indicating that the plume dynamics are close to the strong expansion limit, implying a collisional regime. Through the relation between the estimated values of terminal flow velocity and surface temperature, u_T²∝T_S, it is found that, at low laser fluences, the surface temperature increases linearly with laser fluence, whereas, at the laser fluence at which Si_n clusters are observed, the increase of temperature is below the linear dependence. The population distribution of the ejected Si_n provides some indication of a formation mechanism based on condensation. Analogies between the ablation behavior of silicon monoxide and silicon targets are considered. PACS 82.30.Nr; 81.05.Gc; 78.70.-g     

氨/乙醇混合团簇多光子电离质谱

用多光子电离技术结合飞行时间质谱仪对氨与乙醇混合团簇进行了研究。在脉冲激光波长分别为266,355nm和532nm条件下,仅在355nm作用下观测到团簇离子。主要的电离产物为质子化的（C2H5OH）n（NH3）mH＋（n=0—3,m=0—4）混合团簇离子,且各个序列的离子强度随m的增大而减小。经分析,氨与乙醇混合团簇电离后团簇离子发生内部质子化转移反应是形成质子化团簇离子的主要原因。不同尺寸团簇离子信号强度随电离激光光强变化的光强指数曲线显示,团簇均发生四光子电离过程。通过理论计算得到其中性和离子团簇的稳定结构,解离能,解离通道。并证实团簇发生电离解离时发生了团簇内质子转移反应。     

Two-dimensional imaging of atomic and nanoparticle components in copper plasma plume produced by ultrafast laser ablation

We report on the spatial and temporal evolution of the plume generated during ultrafast laser ablation of a pure copper target with 800 nm, ≈50 fs, Ti: Sapphire laser pulses. Time-gated imaging was used to record 2-dimensional images of plume populations. The temporal evolution of neutral (Cu*), and ionic (Cu⁺) components of the plume are separately imaged by exploiting bandpass interference filters, while nanoparticles are investigated by collecting their characteristic broadband emission. The ionic component of the plume moves two to three times faster than the neutral component, with a velocity which is almost independent of laser fluence. Plume emission intensity variations at different fluences and delay times are studied for both atomic and nanoparticle components.     

Laser ablation mechanism and plume dynamics of polyarylsulfone films studied by laser ionization time-of-flight mass spectrometry

The KrF laser ablation of polyarylsulfone (PAS) was investigated for fluences between 90 and 200 mJ/cm². Neutral fragments were probed using laser post ionization (193 nm) time-of-flight (TOF) mass spectrometry. Decomposition of PAS was found to occur mainly through scission of C-S and C-O bonds as well as via decomposition of the phenylene rings in the chain. The dependencies of both the flight velocities and the Knudsen layer temperature of the fragments on fluence suggest that PAS ablation is a photothermal process. In contrast, the high average translational energies (up to a few tens of eV) indicate the existence of a non-thermal component in the process. In terms of the plume dynamics, the fitting of the arrival profiles of the fragments with a shifted Maxwell-Boltzmann distribution over the full fluence range indicates the existence of a collision during the adiabatic expansion process.     

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     

XeCl-laser-generated ablation products from a nitrogen-rich polymer studied by laser-ionization mass spectrometry

Laser-ionization time-of-flight mass spectrometry has been used to probe laser-ablation products from a nitrogen-rich polymer at a wavelength of 308 nm. The ablation products at a laser fluence of 150 mJ/cm² showed, similar to 532 nm ablation studied previously [18], two strong peaks due to neutral species that were assigned to C⁺ and CN⁺, as well as several weak peaks that were assigned to CH⁺, HCN⁺, HCNH⁺, H_nN–CN⁺ (n=1–3), and H₂N–C=N–CN⁺ or H₂N–C=N–CN⁺. The ablation products at 870 mJ/cm² revealed, in addition to a broad signal due to ionic products generated directly by the ablation laser, several peaks due to neutral products that were assigned to C⁺, C ₂ ⁺ , C ₃ ⁺ , CN⁺, HCN⁺, HCNH⁺, and NCCN⁺. The most probable flight velocities for major neutral products are 5.7×10⁴ cm/s at 150 mJ/cm² and 2.3–2.7×10⁴ cm/s at 870 mJ/cm². The results at a laser fluence of 150 mJ/cm² support the finding that the translational energy of the tragments has importance for the collision-induced product generation in the laser plume, as suggested earlier [18]. Furthermore, the product generation at 870 mJ/cm² is interpreted by the ejection of small neutral and ionic fragments, and subsequent reactions among the fragments.     

1-萘酚团簇的紫外光电离质谱研究

用飞行时间质谱仪和超声速脉冲分子束技术研究了紫外激光对1-萘酚(1HN)团簇的电离质谱.观测到(1HN)_n~+系列的团簇离子,且离子强度随团簇尺寸的增大而减小.电离激光的强度(在5μJ/pulse～100μJ/pulse范围内)对团簇离子强度的相对分布影响较小,说明软电离为产生团簇离子的主要过程,团簇离子的强度分布反映出电离前中性团簇的分布特征.增大电离区的进样气压可以产生更大尺寸的团簇离子,同时在(1HN)_n~+后面观测到新系列的团簇离子.这些新生离子与(H_2O)_m有关,考虑到1-萘酚团簇可以通过OH形成H键,推测该新生团簇离子通过团簇内的反应而产生.     

Pulsed laser ablation of SiC in a nitrogen atmosphere: formation of CN

Optical emission lines from the plasma generated by a laser ablation process have been investigated to gather information on the nature of the chemical species present. In particular, the experiments were carried out during the laser ablation of a ceramic sintered SiC target, both in vacuum and in presence of controlled nitrogen atmosphere. Time integrated and spatially resolved emission spectra are dominated by the atomic emission lines from silicon and carbon species, either neutral, or singly ionized. When the ablation process was carried out in a nitrogen gas background direct evidence of the formation of the CN molecular specie was found. Fast photography imaging of the expanding plume revealed the formation of a shock wave at nitrogen pressure above 13.3 Pa, with the consequent heating of the shocked region and enhancement of the kinetics of ionization and excitation. Since the C₂ specie was absent, a CN formation mechanism involving atomic carbon and nitrogen in the presence of a shock wave is suggested. PACS 52.38.Mf; 52.50.Jm, 47.40.-x     

Phosphorus cluster production by laser ablation

Neutral and charged phosphorus clusters of a wide size range have been produced by pulsed laser ablation (PLA) in vacuum at 532, 337, and 193 nm ablating wavelengths and investigated by time-of-flight mass spectrometry. The neutral P_n clusters are even-numbered with local abundance maxima at n=10 and 14, while the cationic and anionic clusters are preferentially odd-numbered with P₇⁺, P₂₁⁺, and P₁₇^- being the most abundant ions. The dominance of the magic clusters is more pronounced at 337-nm ablation that is explained by efficient direct ejection of their building blocks under these conditions. Nanocrystalline phosphorus films have been produced by PLA in ambient helium gas. PACS 52.38.MF; 61.46.+w; 79.20.Ds; 81.07.B; 81.16.Mk     

VUV laser photoionization of laser-stimulated desorbed species

We report here first results about single-photon VUV laser photoionization of desorbed species from a silicon surface irradiated by a pulsed and tunable UV laser (290-300 nm). The combination of VUV photoionization at 10 eV with laser-induced surface desorption offers a largely non-destructive and sensitive method for quantitative analysis. Indeed it allows mass spectrometry measurements with uniform sensitivity and without breaking the chemical bonds in the probed species. The energy of the VUV photons (9.91 eV) is above the ionization limits of a number of molecules and fragments. Moreover, adjustment of the delay between the desorbing and the probe lasers allows the measurement of the time-of- flight distribution of the ejected species. Data extracted from these measurements are fundamental for a better understanding of laser-surface interaction phenomena.     

Investigation of different liquid media and ablation times on pulsed laser ablation synthesis of aluminum nanoparticles

Aluminum nanoparticles were synthesized by pulsed laser ablation of Al targets in ethanol, acetone, and ethylene glycol. Transmission Electron Microscope (TEM) and Scanning Electron Microscope (SEM) images, Particle size distribution diagram from Laser Particle Size Analyzer (LPSA), UV-visible absorption spectra, and weight changes of targets were used for the characterization and comparison of products. The experiments demonstrated that ablation efficiency in ethylene glycol is too low, in ethanol is higher, and in acetone is highest. Comparison between ethanol and acetone clarified that acetone medium leads to finer nanoparticles (mean diameter of 30 nm) with narrower size distribution (from 10 to 100 nm). However, thin carbon layer coats some of them, which was not observed in ethanol medium. It was also revealed that higher ablation time resulted in higher ablated mass, but lower ablation rate. Finer nanoparticles, moreover, were synthesized in higher ablation times.     

Angular distributions of plume components in ultrafast laser ablation of metal targets

In view of its fundamental interest and relevance to nanoparticle film production, we have characterised the nanoparticle component of the ablation plume generated in femtosecond laser irradiation of metals. The results are compared to those of the ion plume, which is considered as representative of the atomic component. At moderate laser fluences, the angular distributions of both nanoparticle and ionic components were studied by measuring the spatial distribution of deposition on a transparent substrate and with a planar Langmuir probe, respectively. Our results show that both angular profiles of the plume components can be described by Anisimov model of isentropic expansion. As the laser fluence is increased above a value of several times the ablation threshold, the shape of the nanoparticle angular distribution progressively differs from the Anisimov prediction, contrary to what is observed for the ion component. This effect is interpreted in terms of the influence of the pressure exerted by the nascent atomic plasma plume on the initial hydrodynamic evolution of nanoparticle material.     

Cluster generation by laser ablation

We produced niobium clusters over a wide size range (Nb_n: 1≤n≤1000) by a laser ablation method in a low-pressure condensation source. Mass spectra of the neutral clusters, positive and negative ion clusters were measured by a time-of-flight mass spectrometer with a high mass resolution and a wide mass range. Similarity and difference in their mass spectra were examined to understand the cluster generation process in different charged states.     

Mechanism of ablation of CdS at laser wavelengths in the visible and in the UV

The mechanisms of laser ablation of CdS targets at different laser wavelengths have been investigated. (CdS)_n⁺ cluster formation is only observed upon 532 nm ablation. The time and energy distributions of neutral S, S₂, Cd and CdS show significant dependence on laser wavelength. Bimodal distributions are observed at 266 and 308 nm. For the former, the average kinetic energy increases significantly with mass, taking values in the range of 0.3-1.7 eV. At 308 nm the slow component of the time distribution disappears at distances above the target larger than 1 cm. At this wavelength, the observed time distribution appears to reflect mainly the dynamics of the expansion. At 532 nm the time distribution is monomodal and the average kinetic energies are below 0.2 eV. Clear indications of the participation of thermal (at 532 nm) and non-thermal mechanisms (at 266 nm) have been found. It is tentatively concluded that the cluster formation observed upon ablation at 532 nm can be related to the thermal ablation mechanisms in which the low kinetic energy of the species in the plume and their similar velocities favor the aggregation processes.     

Cluster-assisted generation of multicharged ions in nanosecond laser ionization of carbon bisulfide clusters at 1064nm

The photoionization of seeded carbon bisulfide molecular beam by a 1064\,nm nanosecond Nd-YAG laser with intensities varying from $0.8\times10^{11}$ to $5.6\times10^{11}$\,W/cm$^{2}$ have been studied by time-of-flight mass spectrometry. Multiply charged ions of S$^{q + }$ ($q$ = 2--6) and C$^{q +}$ ($q$ = 2--4) with kinetic energy of hundreds of electron volts have been observed, and there are strong experimental evidences indicating that those multicharged ions originate from the ionization of CS$_{2}$ neat clusters in the beam. An electron recolliding ionization model is proposed to explain the appearance of those multiply charged atomic ions under such low laser intensities.     

Emission properties of laser ablation of SnO2: Sb transparent conducting film and KTiOPO4 crystal

Optical emission spectra of Nd:YAG laser ablation of KTiOPO₄ (KTP) crystal and SnO₂:Sb transparent conducting thin film were recorded and analyzed in vacuum and in air. The integral intensities of spectral lines from laser-ablated KTP crystal were obtained as functions of distance from the target surface and laser power density in vacuum and in air. The ambient gas effects on pulsed laser ablation of target were discussed. We also performed laser ablation of SnO₂:Sb transparent conducting thin film in air and the electron temperature and full-width at half-maximum (FWHM) of atomic and ionic spectral lines in the plasma were quantified using Boltzmann plot method and Lorentzian fit, respectively. Integral intensities of atomic and ionic Sn spectral lines were also obtained as functions of distance from the target surface and laser irradiance. The intensity ratio of ionic and atomic Sn spectral lines as a function of laser power density was got which gives some information about the variation of ionization ratio with laser irradiance in the plasma produced by high-power laser.     

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.     

Photoablation of polyurethane films using UV laser pulses

Pulsed ultraviolet laser ablation of two polyurethane films has been studied in terms of ablation rate behaviour and time-of-flight mass spectroscopy of the positively charged photofragments. Three excimer laser wavelengths (193, 248 and 308 nm; 17–30 ns pulse duration) and short-pulse laser system (pulse duration 500 fs or 5 ps, at 248 nm) were employed. The results of the influence of energy fluence on the ablation rate are tested against other photoablation models and a table of fitted physical constants is presented. The upper limit of the mean activation energy for desorption is found to be considerably lower than the energy required to break single covalent bonds. The mass analysis of the positively charged species produced during the photoablation process provides valuable insight into the photofragmentation mechanism.