Laser Ablation Molecular Isotopic Spectrometry: Parameter influence on boron isotope measurements

Laser Ablation Molecular Isotopic Spectrometry (LAMIS) was recently reported for optical isotopic analysis of condensed samples in ambient air and at ambient pressure. LAMIS utilizes molecular emissions which exhibit larger isotopic spectral shits than in atomic transitions. For boron monoxide ¹⁰BO and ¹¹BO, the isotopic shifts extend from 114 cm⁻¹ (0.74 nm) to 145–238 cm⁻¹ (5–8 nm) at the B²Σ⁺ (v = 0) → X²Σ⁺ (v = 2) and A²Π_i (v = 0) → X²Σ⁺ (v = 3) transitions, respectively. These molecular isotopic shifts are over two orders of magnitude larger than the maximum isotopic shift of approximately 0.6 cm⁻¹ in atomic boron. This paper describes how boron isotope abundance can be quantitatively determined using LAMIS and how atomic, ionic, and molecular optical emission develops in a plasma emanating from laser ablation of solid samples with various boron isotopic composition. We demonstrate that requirements for spectral resolution of the measurement system can be significantly relaxed when the isotopic abundance ratio is determined using chemometric analysis of spectra. Sensitivity can be improved by using a second slightly delayed laser pulse arriving into an expanding plume created by the first ablation pulse.     

Bimodal Nanoparticle Size Distributions Produced by Laser Ablation of Microparticles in Aerosols

Silver nanoparticles were produced by laser ablation of a continuously flowing aerosol of microparticles in nitrogen at varying laser fluences. Transmission electron micrographs were analyzed to determine the effect of laser fluence on the nanoparticle size distribution. These distributions exhibited bimodality with a large number of particles in a mode at small sizes (3–6-nm) and a second, less populated mode at larger sizes (11–16-nm). Both modes shifted to larger sizes with increasing laser fluence, with the small size mode shifting by 35% and the larger size mode by 25% over a fluence range of 0.3–4.2-J/cm². Size histograms for each mode were found to be well represented by log-normal distributions. The distribution of mass displayed a striking shift from the large to the small size mode with increasing laser fluence. These results are discussed in terms of a model of nanoparticle formation from two distinct laser–solid interactions. Initially, laser vaporization of material from the surface leads to condensation of nanoparticles in the ambient gas. Material evaporation occurs until the plasma breakdown threshold of the microparticles is reached, generating a shock wave that propagates through the remaining material. Rapid condensation of the vapor in the low-pressure region occurs behind the traveling shock wave. Measurement of particle size distributions versus gas pressure in the ablation region, as well as, versus microparticle feedstock size confirmed the assignment of the larger size mode to surface-vaporization and the smaller size mode to shock-formed nanoparticles.     

强流脉冲离子束辐照靶材烧蚀效应二维数值研究

对强流脉冲离子束(IPIB)辐照Ti靶的烧蚀效应进行了二维数值研究.得到了表面烧蚀物质随脉冲时间的变化关系.得出TEMP Ⅱ 型加速器产生的脉冲束流辐照靶材时引起的汽、液化均是从表面开始、并且汽化过程中表面物质被层层烧蚀的结论.同时，得到中心区的平均烧蚀速度为10m/s 数量级，它远小于产生的烧蚀等离子体的喷发速度.得到脉冲期间靶材内部不同位置烧蚀斑痕形状的时间演化过程，以及束流中含有的离子种类分额不同时IPIB辐照过程产生的不同效果. 关键词： 强流脉冲离子束 靶 烧蚀过程 二维数值模拟     

Dynamics of radiation scattering by particles of condensed phase in quasicontinuous laser irradiation of metals

Radiation scattering by particles of condensed phase in an ablation plasma plume has been experimentally studied during quasicontinuous laser irradiation (λ = 1.06 μm, q = 0.1–9 MW/cm², τ ∼ 1.5 msec) of duraluminum D16T, aluminum A99, and bismuth. The particle size distribution and the nature of their dispersal during irradiation was studied in scattered light (λ = 0.69 μm) from individual particles that could be visually observed on photographs. It was found that under the pressure developed in the plume, large particles ejected from the irradiated zone can move backward and return to the target (D16T). The plume (Bi) becomes brighter due to ablation of particles in the path of the laser beam. The directional scattering coefficients for scattering from the local zone on the axis of the plume, measured during the laser pulse, were used to study the relationship between the dynamics of entry of condensed phase into the plume, shielding of the target by the particles, and brightening of the plume under the action of the incident laser radiation. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 2, pp. 210–219, March–April, 2006.     

Laser ablation synthesis of monodispersed magnetic alloy nanoparticles

Monodispersed CoPt alloy nanoparticles were synthesized by a pulsed laser ablation (PLA) technique coupled with a low-pressure operating differential mobility analyzer (LP-DMA). The CoPt alloy nanoparticles were generated by laser ablating a solid Co–Pt target. In CoPt alloy nanoparticles synthesized from a target with a Co composition of 75 at%, the nanoparticle surfaces were covered by an oxide layer and exhibited a core-shell structure. In contrast, no shell was observed in particles generated from a target with a Co:Pt ratio of 50:50 at%. According to an EDX analysis, the compositions of the individual nanoparticles were almost the same as that of the target material. Finally, the magnetic hysteresis loops of the CoPt alloy nanoparticles exhibited ferromagnetism.     

High resolution laser spectroscopy of the titanium monohalides, TiCl and TiBr

The electronic spectra of the titanium monohalides, TiCl and TiBr, have been investigated in the blue-violet region using a laser ablation molecular beam spectrometer. Five subbands assigned as ⁴Γ_5/2-X⁴Φ_3/2 (0, 0), ⁴Γ_5/2-X⁴Φ_3/2 (1, 1), ⁴Γ_5/2-X⁴Φ_5/2 (0, 0), ⁴Γ_7/2-X⁴Φ_5/2 (0, 0) and ⁴Γ_7/2-X⁴Φ_7/2 (0, 0) were observed and recorded at both low and high-resolution for titanium monochloride. A Hund’s case (a) rotational analysis has been carried out for the ⁴⁸Ti³⁷Cl and ⁴⁸Ti³⁵Cl isotopic species, and polynomial analyses for these, as well as the ⁴⁶Ti³⁵Cl, ⁴⁷Ti³⁵Cl, ⁴⁹Ti³⁵Cl, and ⁵⁰Ti³⁵Cl isotopologues have been completed. The same spectral region yielded several molecular transitions for titanium monobromide, 10 of which were recorded at high resolution. Six of these have been attributed to a ⁴Γ-X⁴Φ electronic transition at 23 484 cm⁻¹, while the remaining four have been assigned to a second ⁴Γ-X⁴Φ electronic transition at 23 613 cm⁻¹. A Hund’s case (a) global analysis has been carried out for the ⁴⁸Ti⁷⁹Br and ⁴⁸Ti⁸¹Br isotopologues.     

Al原子共振双线跃迁几率实验研究

我们用Nd：YAG脉冲激光烧蚀金属Al靶产生等离子体，利用时间分辨技术摄取Al等离子体辐射时间分辨谱，获得Al原子共振双线辐射谱；通过积分谱线下的面积，计算共振双线强度；根据共振双线强度比，推断Al原子共振双线跃迁几率比，并与理论计算结果比较。结果发现，实验结果与理论计算符合的很好。     

Particle number density and velocity distributions in laser plumes

A time-of-flight mass spectrometer with electron impact ionization facility was used in investigations of the laser plume structure. Densities and velocity distributions of positively charged and neutral species were measured 12 cm downstream of the target. Velocities of particles in a plume were measured by the retarding potential method. The combination of a skimmer and declining electric field was used to suppress the influence of charged particles during the measurement of the neutral component parameters. In the case of YBaCuO ceramic laser ablation, a strong variation of the laser-induced plume composition was observed from its head to its tail. It seems to be accounted for by the difference of the starting (phase transition) temperatures of various layers of a plume. Ions detected mainly in the head of a plume were followed by atoms, molecules and clusters in inverse succession to their appearance in the plume under the light intensity increase. The characteristic of the number density dependence upon the laser spot diameter make it clear that most of the molecules BaO and YO are the direct product of ablation. In contrast, the detected clusters with masses up to 2000 amu are the product of condensation in the expanding plume under the conditions of the experiments.     

Investigation of nanoparticle generation during femtosecond laser ablation of metals

The production of nanoparticles via femtosecond laser ablation of gold and copper is investigated experimentally involving measurements of the ablated mass, plasma diagnostics, and analysis of the nanoparticle size distribution. The targets were irradiated under vacuum with a spot of uniform energy distribution. Only a few laser pulses were applied to each irradiation site to make sure that the plume expansion dynamics were not altered by the depth of the laser-produced crater. Under these conditions, the size distribution of nanoparticles does not exhibit a maximum and the particle abundance monotonously decreases with size. Furthermore, the results indicate that two populations of nanoparticles exist within the plume: small clusters that are more abundant in the fast frontal plume component and larger particles that are located mostly at the back. It is shown that the ablation efficiency is strongly related to the presence of nanoparticles in the plume.     

Quantitative analysis of original and powdered rocks and mineral inclusions by laser ablation inductively coupled plasma mass spectrometry

Direct analysis of rocks by laser ablation inductively coupled plasma mass spectrometry is described. Both powdered standard rocks and the original rocks were analysed and the results agreed with each other in spite of the difference in the surface states. Microprobe analysis of biotite in granite JG1 was also done directly with a focused laser beam and the results obtained were very close to the solution values given by the conventional aqueous method using biotite separated from an original rock. For quantitative analysis, the measured signal intensity was normalized either by the ablated weight or the barium signal intensity. Forty-two major and minor elements (two of them being used as internal standards) in twelve standard rocks fromt the igneous rock series of the Geological Survey of Japan were determined successfully.