Vapour and plasma ignition thresholds for visible pulsed-laser ablation of metallic targets

The coupling of visible nanosecond laser pulses to metallic targets irradiated in vacuum is studied. The expressions of the vapour and plasma ignition times are obtained. Two cases for vapour breakdown in the plasma ignition process are considered. The first case is that 40 generations of new electrons are born in vapour generation time before plasma formation as assumed in the literature. The second case is that 10 generations of new electrons are born in vapour generation time. Molybdenum (Mo), niobium (Nb) and aluminium (Al) targets are considered for illustrations of our results. The expression of the plasma ignition time for the Al target is substantially different from that reported in the literature. The vapour and plasma ignition threshold laser intensities are calculated and compared with those reported in the literature. Reasons for disagreement are discussed. The plasma ignition threshold estimated in the second case is noted to be in good agreement with the reported experimental result.     

The agglomeration state of nanosecond laser-generated aerosol particles entering the ICP

Fundamental understanding of aerosol formation and particle transport are important aspects of understanding and improving laser-ablation ICP–MS. To obtain more information about particles entering the ICP, laser aerosols generated under different ablation conditions were collected on membrane filters. The particles and agglomerates were then visualised using scanning electron microscope (SEM) imaging. To determine variations between different sample matrices, opaque (USGS BCR-2G) and transparent (NIST SRM 610) glass, CaF₂, and brass (MBH B26) samples were ablated using two different laser wavelengths, 193 and 266 nm. This study showed that the condensed nano-particles (∼10 nm in diameter) formed by laser ablation reach the ICP as micron-sized agglomerates; this is apparent from filters which contain only a few well-separated particles and particle agglomerates. Ablation experiments on different metals and non-metals show that the structure of the agglomerates is matrix-dependent. Laser aerosols generated from silicates and metals form linear agglomerates whereas particle-agglomerates of ablated CaF₂ have cotton-like structures. Amongst other conditions, this study shows that the absorption characteristics of the sample and the laser wavelength determine the production of micron-sized spherical particles formed by liquid droplet ejection.     

用大芯径石英玻璃光纤传输兆瓦级高能激光脉冲及其在双波长LA-LIBS技术中的应用

为了解决单脉冲激光诱导击穿光谱(LIBS)技术在元素分析时空间分辨本领与分析灵敏度之间的矛盾,本文利用一台双波长输出的Nd∶YAG激光器开展了双波长激光剥离-激光诱导击穿光谱(LA-LIBS)技术的研究。其中532 nm的二倍频激光用于剥离样品;1 064 nm的基频激光通过大芯径石英玻璃光纤传输并实现一定的延时后用于击穿被剥离的样品。两束激光采用正交几何配置以实现高空间分辨高灵敏的元素分析。实验研究了1 064 nm激光到光纤的耦合、光纤输出后的准直以及再聚焦时的一些关键技术问题。研究并得出了四种不同光纤对激光能量的传输能力。选择利用芯径为800 μm,数值孔径为0.39、长50 m的石英玻璃光纤成功传输了15 mJ的调Q激光脉冲并实现了250 ns的延时。并在此基础上开展了铜合金样品的双波长LA-LIBS分析,实验验证了基于一台Nd∶YAG激光器开展双波长LA-LIBS研究的可行性。该技术只需要一台激光器就可以完成相应的光谱分析,具有系统结构简单,便于小型化等优点,适合对不同样品开展原位的高空间分辨高灵敏的元素显微分析。     

银饰品中铜杂质含量的激光剥离—激光诱导击穿光谱定量分析

正交双波长双脉冲的激光剥离—激光诱导击穿光谱技术能够在较少样品烧蚀的前提下获得高的光谱分析灵敏度,因此该技术可以从根本上解决在单脉冲激光诱导击穿光谱技术中空间分辨本领与光谱分析灵敏度之间的矛盾。为了消除在该光谱技术中的实验参数对光谱信号强度及其定量分析结果的影响,实验研究了银饰品中杂质铜的光谱信号与银元素的光谱信号的相关性。研究结果表明：324.75 nm的铜原子辐射线与328.07 nm的银原子辐射线的强度呈很高的线性相关性,因此选择以银328.07 nm的光谱线作为内标线,采用内标法就可以消除双光束激光的空间几何配置以及剥离激光脉冲能量等实验参数对铜原子辐射信号的影响,从而可以采用正交双波长双脉冲激光剥离——激光诱导击穿光谱技术开展银饰品中铜杂质含量的定量分析。选择银328.07 nm的光谱线作为内标线,基于内标法建立了铜的校正曲线。当激光烧蚀坑洞直径约为17 μm时, 当前实验条件下银饰品中铜元素的检出限可以达到44 ppm。     

Determination of rare earth element in carbonate using laser-ablation inductively-coupled plasma mass spectrometry: an examination of the influence of the matrix on laser-ablation inductively-coupled plasma mass spectrometry analysis

In this study, we examined the influence of the matrix on rare earth element (REE) analyses of carbonate with laser-ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) using carbonate and NIST glass standards. A UV 213 nm Nd:YAG laser system was coupled to an ICP-MS. Laser-ablation was carried out in both He and Ar atmospheres to investigate the influence of ablation gas on the analytical results. A small amount of N₂ gas was added to the carrier gas to enhance the signal intensities. Synthetic CaCO₃ standards, doped with REEs, as well as NIST glasses (NIST SRM 610 and 612) were used as calibration standards. Carbonatite, which is composed of pure calcite, was analyzed as carbonate samples. The degree of the influence of the matrix on the results was evaluated by comparing the results, which were calibrated by the synthetic CaCO₃ and NIST glass standards. With laser-ablation in a He atmosphere, the differences between the results calibrated by the synthetic CaCO₃ and NIST glass standards were less than 10% across the REE series, except for those of La which were 25%. In contrast, for the measurements made in an Ar atmosphere, the results calibrated by the synthetic CaCO₃ and NIST glass standards differed by 25-40%. It was demonstrated that the LA-ICP-MS system can provide quantitative analysis of REE concentrations in carbonate samples using non matrix-matched standards of NIST glasses.     

Analysis of rare-earth elements in soil sample by using laser-ablation ion trap mass spectrometry

Laser-ablation ion trap mass spectrometry (LA-ITMS) is applied for the analysis of rare-earth elements in soil samples. The target elements studied in this work were ytterbium (Yb) and samarium (Sm). The isotopic compositions of these elements were analyzed for standard samples with chip shape, the western phosphate rock sample (NIST SRM-694), and soil samples collected near our laboratory. For metal samples of Sm and Yb, isotopes of these elements as well as oxide forms were clearly identified. For the case of soil samples only a tentative assignment on the mass peaks were performed due to the complicated mass spectra that originated from the oxide forms of various rare-earth elements.     

Synthesis of nano-structured materials by laser-ablation and their application to sensors

We describe the synthesis of nano-structured materials of ZnO and Pd by laser ablation and their applications to sensors. The synthesis of ZnO nano-wires was performed by nano-particle assisted deposition (NPAD) where nano-crystals were grown with nano-particles generated by laser-ablating a ZnO sintered target in an Ar background gas. The synthesized ZnO nano-wires were characterized with a scanning electron microscopy and the photoluminescent characteristics were examined under an excitation with the third harmonics of a Nd:YAG laser. The nano-wires with a diameter in the range from 50 to 150 nm and a length of up to 5 μm were taken out of the substrate by laser blow-off technique and/or sonication. It was confirmed that the nano-wires showed the stimulated emission under optical pumping, indicating a high quality of the crystalinity. Pd nano-particles were generated by laser-ablating a Pd plate in pure water. The transmission electron microscope observation revealed that Pd nano-particles with a diameter in the range from 3 nm to several tens of nanometers were produced. Using these nano-structured materials, we successfully fabricated sensors by the dielectrophoresis techniques. In the case of the ultraviolet photosensor, a detection sensitivity of 10 nW/cm² was achieved and in the case of hydrogen sensing, the response time of less than 10 s has been demonstrated with Pd nano-particles.     

用高重频激光剥离-火花诱导击穿光谱分析铝合金样品

为了提高基于等离子体原子发射光谱元素分析技术的分析速度,在高重复频率的前提下建立了一套激光剥离-火花诱导击穿光谱元素分析系统并以铝合金为样品开展了光谱分析。实验以低脉冲能量的声光调Q固体激光脉冲剥离样品,并触发高压火花放电以增强等离子体辐射、提高光谱分析灵敏度。研究结果表明： 在高重频火花放电的作用下,等离子体辐射的峰值强度和弛豫时间分别得到了增强和延长,信号的时间积分强度增强因子可以达到1～2个数量级,且更易于实现时间分辨的信号检测。对铝合金中微量铬元素分析的检出限可达~132 ppm。该研究验证了高重频激光剥离-火花诱导击穿光谱用于分析固体样品元素的可行性,其技术有望在固体样品元素的快速分析中发挥一定的作用。该光谱技术能同时兼顾扫描成像的速度、空间分辨率和光谱分析灵敏度,并为固体样品的二维或者三维元素分布的高分辨快速扫描成像分析提供了一种很好的技术途径。