激光感生击穿光谱技术（LIBS）的原理及影响因素

激光感生击穿光谱技术（LIBS）具有不需制备样品,快速分析,可进行实时控制的特点显示了巨大实际应用价值,文中介绍了激光感生击穿光谱技术（LIBS）的发展历史、研究现状及其原理。同时通过重复频率为20 Hz,最高单脉冲能量为50　mJ的纳秒激光（10 ns,1　064 nm）研究了在不同激发条件下Cr和Co薄膜产生的光谱信号。得出对于Cr膜当激发能量小于10 mJ时,信号差异不明显。但是当激发能量超过10　mJ时将产生明显的变化。分析了激光特性、延迟时间、实验装置、环境气体的种类及压力、单/双脉冲、以及采用的理论分析方法对LIBS探测结果的影响。     

Double pulse UV laser induced breakdown spectroscopy of stainless steel

Results of experimental investigations of 304 austenitic stainless steel (ASS) ultraviolet spectral range by single and double pulse laser induced breakdown spectroscopy (LIBS) at atmospheric pressure are reported. Various parameters, such as laser energy, placement of the laser beam focus with respect to the surface of illumi-nation, and collinear double laser pulse delay were used as variables. This study contributes to a better under-standing of the LIBS plasma dynamics by observing the temporal evolution of various emission lines. Temperature measurements were made by the Boltzmann diagram method using singly ionized Fe lines, and electron densities were found from Stark broadening. The temporal behaviors of these parameters were also estimated. It was found that the electron temperature for double pulses is higher than that for single pulse of the same total energy. For double pulse LIBS, the iron line emission intensities are enhanced and the analytical performance is improved. For instance, the intensity of iron line Fe I 275.01 nm was a factor of about 300 times higher if a double pulse of 2 × 20 mJ was used instead of a single pulse of 40 mJ when focusing the beam 4.7 mm behind the target surface. Published in Zhurnal Prikladnoi Spektroskopii, Vol. 79, No. 5, pp. 654–660, 2006.     

用光电双脉冲LIBS技术快速测量水中痕量汞元素

用木片吸收水溶液,将水溶液样品转变为固体样品,从而解决用激光诱导击穿光谱(LIBS)技术直接分析水样品所带来的诸多问题,并首次采用光电双脉冲LIBs技术来增强激光等离子体中汞的原子辐射.实验绘制了用单脉冲LIBS技术和光电舣脉冲LIBS技术所得到的汞的校正曲线并得出这两种技术中汞的最低检出限分别为2.4和0.3 mg·...     

A spectroscopic analysis study of graphite using laser technique

Results of single and double pulses (SP- and DP) Q-switch Nd:YAG laser induced breakdown spectroscopy (LIBS) at atmospheric pressure on the structure of graphite target are reported. Various parameters, such as laser energy, placement of the focus with respect to the surface of illumination, and time delay between laser pulse and ICCD camera pulse were used as variables. This study contributes to a better understanding of the LIBS plasma dynamics of the SP- and DP effect by observing the temporal evolution of emission line of graphite. The gate width and the delay time were adjusted to achieve the best possible signal to noise ratio. Electron densities were found from Stark broadening. The temporal behavior of the last one was also estimated. It was found that the electron density for DP of 2 × 20 mJ is higher than that for SP of 40 mJ of the same total energy. The results show a faster decay of continuum, spectral lines, and a shorter plasma life.     

实验参数对激光诱导铝合金产生等离子体光谱的影响

利用Nd∶YAG脉冲激光诱导击穿2519A铝合金产生等离子体光谱,采用光谱仪检测和记录了Al和Cu的原子谱线,并研究了不同实验参数或条件对该谱线的影响。结果表明,透镜到样品表面距离、探测角度、激光脉冲能量、观测高度和环境气压大小对实验分析性能,如谱线强度、信背比和实验可重复性等均有较大的影响,通过设置适当的实验条件可以获得最佳的实验结果。     

Titanium plasma spectroscopy studies under double pulse laser excitation

Laser-induced breakdown spectroscopy (LIBS) was applied for parametric studies of titanium (Ti) plasma using single and double pulsed laser excitation scheme. Here a pulsed Nd:YAG laser was employed for generation of laser produced plasma from solid Ti target at ambient pressure. Several ionized titanium lines were recorded in the 312–334 nm UV region. The temporal evolution of plasma parameters such as excitation temperature and electron number density was evaluated. The effect of incident laser irradiance, position of the laser beam focal point with respect to the surface of illumination, single and double laser pulse effect on plasma parameters were also investigated. This study contributes to a better understanding of the LIBS plasma dynamics of the double laser pulse effect on the temporal evolution of various Ti emission lines, the detection sensitivity and the optimal dynamics of plasma for ionized states of Ti. The results demonstrate a faster decay of the continuum and spectral lines and a shorter plasma life time for the double pulse excitation scheme as compared with single laser pulse excitation. For double pulse excitation technique, the emissions of Ti lines intensities are enhanced by a factor of five which could help in the improvement of analytical performance of LIBS technique. In addition, this study proved that to avoid inhomogeneous effects in the laser produced plasma under high laser intensities, short delay times between the incident laser pulse and ICCD gate are required.     

液相基质中重金属元素激光诱导击穿光谱实验参数的优化

针对混合溶液中重金属元素的激光诱导击穿光谱(LIBS)测量系统,为提高测量系统的检测灵敏度,以提高混合溶液中Ca和Cr金属元素LIBS光谱线强度的信噪比为目标,对LIBS测量系统中的激光脉冲能量、液相样品流速、ICCD门宽、延时等实验参数进行了优化,得到最优化参数激光脉冲能量、样品流速、ICCD门宽、延时分别为35 m J、30 ml/min、1400 ns和2400 ns,为降低LIBS技术应用于混合溶液中痕量重金属元素的检出限提供了实验参数支撑.     

Effect of ambient conditions on laser-induced breakdown spectra

The role of different ambient conditions on LIBS signal intensity was investigated for better understanding and performance of LIBS as a quantitative and qualitative analytical technique. For this purpose, the relative LIBS signal intensities were measured for a standard Cr line (520.8 nm) at different gas pressures of Ar, He, and air. The plasma was generated using a Q-switched pulsed Nd:YAG laser having wavelength of 1064 nm and pulse duration of 8 ns. The analysis revealed that the intensities of the spectral atomic Cr line (520.8 nm) were strongly enhanced under the argon environment in 10?C40 mbar range. The electron excitation temperature (T _e ) and number density (n _e ) were estimated by using a Boltzmann plot and a Stark broadening profile, respectively. For optimum dependence of LIBS, laser energy and pressure dependence was also studied. The electron temperature and number density showed an increase with increase in ambient gas pressure.     

合金钢的激光诱导击穿光谱实验条件优化

利用1 064 nm波长Nd∶YAG脉冲激光诱导击穿合金钢产生激光等离子体光谱,采用高分辨率及门宽控制的ICCD探测LIBS信号光谱。选用铁元素原子谱线404.581,414.387,427.176和438.355 nm进行分析,研究了不同实验参数对LIBS光谱信号强度的影响结果。实验结果表明,激光脉冲能量、激光聚焦位置以及ICCD探测器的延时等实验参数对合金钢LIBS信号有较大影响。通过优化这些实验参数,获得高光谱强度和信背比的LIBS信号,确定了LIBS技术用于合金钢微量元素成分分析的最佳实验条件,从而开展合金钢样品成分分析。     

Na_2SO_4溶液激光拉曼/激光诱导击穿光谱联合探测

光谱技术应用于海底极端环境下多参数、多相态、无接触探测已成为深海化学传感器发展的一个重要方向,尤其是水下激光拉曼光谱技术和水下激光诱导击穿光谱技术正成为目前研究开发的热点。该工作旨在探索一项水下激光诱导击穿光谱与激光拉曼光谱(LIBS-LRS)联合探测技术,以实现LIBS和拉曼两种检测技术在检测系统上的整合,在信息获取上的互补。在实验室搭建了一套LIBS-LRS联合探测装置,该装置对于拉曼和LIBS采用同样的激发光源、光谱仪和探测器,前置光路分为两部分:拉曼光路和LIBS光路,分别收集Na_2SO_4溶液的拉曼信号和LIBS信号。前置光路收集的拉曼和LIBS信号由Y型光纤导入光谱仪,分别在面阵CCD不同区域进行探测。利用该装置对配置的Na_2SO_4溶液进行探测,同时获得了Na元素的LIBS信号和SO~(2-)_4拉曼信号。另外,随着激光能量的提高,在532nm脉冲激光能量超过3.6mJ时,在拉曼光路同时获得了Na元素的LIBS信号和SO~(2-)_4拉曼信号,这样采用同一光路即可实现两种光谱技术的联合,然而实验发现,随着激光能量的增加,激光在溶液中击穿产生的轫致辐射造成了光谱探测基线整体的抬升,对拉曼光谱弱信号的探测是不利的。实验结果初步证明了在拉曼和LIBS在水下联合探测的可行性。     

新型便携式激光诱导击穿光谱系统综述

本文主要综述了国内外便携式激光诱导击穿光谱(LIBS)系统的研究进展和应用情况。目前该系统主要针对金属元素进行检测,对非金属等轻元素的定量分析需要较大能量的激光激发,但受限于激光器和光谱仪等组件体积的影响,研发便携式、高精度LIBS系统有较高难度。本文针对全元素检测便携设备的研发,利用限域和高压放电脉冲得到了增强的LIBS信号,降低了激光能量,从物理机理上给出了便携式LIBS设备研发的新方向。     

钾元素单脉冲和双脉冲激光诱导击穿光谱研究

基于自行研制的新型液体射流的激光诱导击穿光谱(LIBS)实验装置,研究了实验条件(如积分延时、脉冲间隔、激光能量等)对K元素单脉冲LIBS和双脉冲LIBS等离子发射的影响.实验得知相对单脉冲激光激发,双脉冲激光激发可以显著提高等离子体发射谱线强度,增加谱线强度的衰减时间,提高LIBS数据的稳定性.通过最佳实验条件下K766.49nm谱线强度随溶液浓度的分析,得到该实验系统中,双脉冲激光激发时K元素的检测灵敏度和检测限约是单脉冲激光激发时的37倍.实验结果为双脉冲LIBS技术应用于水体金属的检测提供了一定依据.     

钾元素单脉冲和双脉冲激光诱导击穿光谱研究

基于自行研制的新型液体射流的激光诱导击穿光谱(LIBS)实验装置,研究了实验条件(如积分延时、脉冲间隔、激光能量等)对K元素单脉冲LIBS和双脉冲LIBS等离子发射的影响.实验得知相对单脉冲激光激发,双脉冲激光激发可以显著提高等离子体发射谱线强度,增加谱线强度的衰减时间,提高LIBS数据的稳定性.通过最佳实验条件下K766.49nm谱线强度随溶液浓度的分析,得到该实验系统中,双脉冲激光激发时K元素的检测灵敏度和检测限约是单脉冲激光激发时的37倍.实验结果为双脉冲LIBS技术应用于水体金属的检测提供了一定依据.     

基于常规组合光谱仪下的LIBS快速铅检测研究

激光诱导击穿光谱技术(LIBS)是一种实时在线的无损检测技术,可以满足工农业生产以及生物医学领域检测仪器高速化和自动化的要求。采用波长为1 064 nm的调Q脉冲为激发光源,常规组合光谱仪中的CCD为探测器,以纯铅、玻璃、焊锡等为样品,在建立的LIBS实验装置上对样品的铅含量进行定性定量检测。通过对不同铅含量样品的检测,初步确定了在自行搭建的全国产化系统下,铅的检测极限为0.0074%,定量检测误差多在4%左右,2～3 min即可完成定性定量分析。实验结果表明,采用光栅光谱仪和非增强型CCD完全可以实现LIBS的快速铅检测,其检测极限和检测精度基本达到了商用标准,并大大降低了实验装置成本,对LIBS在国内同行的相关实用化研究具有一定的借鉴作用。     

Double-pulse laser-induced breakdown spectroscopy for trace element analysis in sintered iron oxide ceramics

Double-pulse laser-induced breakdown spectroscopy (LIBS) is an emerging technique for accurate compositional analysis of many different materials. We present a systematic study of collinear double-pulse LIBS for analysis of the trace and side elements boron, manganese, copper, aluminum, titanium, silicon, chromium, nickel, potassium, and calcium in sintered iron oxide targets. The samples were ablated in air by single-pulse and double-pulse Nd:YAG laser radiation (6 ns pulse duration, laser wavelength of 532 nm) and spectra were recorded with an Echelle spectrometer equipped with an ICCD camera. We investigated the evolution of atomic and ionic line emission intensities for different interpulse delay times between the laser pulses (from 100 ns to 50 μs) and gate delays after the second laser pulse. We also varied the energy partition between the first and second laser pulse and the size of the irradiated spot at the sample surface. For the trace and side elements, we observed double-pulse LIBS signals that were enhanced as compared to single-pulse measurements depending on the interpulse delay time, the energy partition between the pulses, and the spot size. For the elements boron, copper, aluminum, titanium, chromium, potassium, and calcium limits of detection below 10 ppm were achieved.     

水溶液中金属元素的激光诱导击穿光谱的检测分析

文章对竖直流动的CuSO₄和Pb(NO₃)₂水溶液样品表面的激光诱导击穿光谱的（简称LIBS）特性进行了观测分析。实验中采用的烧蚀激光波长为532 nm,脉冲宽度为10 ns,重复频率为10 Hz;LIBS信号的探测通过一色散相加型双光栅单色仪、Boxcar和PMT的组合来完成。通过对水溶液中金属元素的LIBS信号随时间和能量演化规律的分析,初步确定了系统 的最佳烧蚀能量和最佳探测延时。受样品表面附近空气击穿时氧元素信号的影响,实验对Cu和Pb各自的击穿位置进行了优化。在分析影响LIBS光谱探测因素的基础上,进一步优化了系统的工作条件和探测 参数。通过对不同浓度下LIBS信号的探测分析,初步确定了系统对Cu与Pb的最低检测浓度,分别约为31,50 ppm(μg·mL-1)。文章还对将LIBS技术运用到海水中重金属的实时在线检测的可 行性进行了讨论。     

金纳米与磁场作用下LIBS检测灵敏度改善研究

针对激光诱导击穿光谱技术（LIBS）中等离子体的发射光谱增强问题,提出一种磁场增强LIBS与纳米颗粒增强LIBS（NELIBS）相结合的方法。采用热蒸发法在样品表面沉积一层直径20 nm的金纳米颗粒。利用波长为1 064 nm,最大能量为200 mJ的Nd∶YAG脉冲激光器在室温,一个标准大气压下对纯铜和黄铜进行诱导击穿。调整激光能量为30~110 mJ,分别使用传统LIBS、磁场增强LIBS、NELIBS以及两种方法结合对纯铜进行激光诱导击穿,得到特征谱线(Cu Ⅰ 521.8 nm)的强度增强因子和信噪比,并对其增强机理进行分析。在相同环境下使用四种方式对黄铜和纯铜进行诱导击穿以探测样品中的微量元素。当在样品表面沉淀金纳米颗粒或者将沉淀有金纳米颗粒的样品放在磁场中进行诱导击穿时,发现纯铜样品的光谱中存在Mg元素的特征谱线Mg Ⅱ 279.569 nm,黄铜样品的光谱中存在Si元素的特征谱线 Si Ⅰ 251.611 nm。实验结果表明：单独施加磁场约束或增加纳米金颗粒均可以有效增强等离子体光谱强度,但增强效果弱于两种方法结合,磁场约束对光谱的增强效果弱于NELIBS的增强效果。当结合NELIBS与磁场约束LIBS时,谱线增强因子最高可达14.3(Cu Ⅰ 521.8 nm),相比于磁场增强LIBS和NELIBS,最大增强因子分别提高了28%和59%。四种情况中当激光脉冲能量逐渐增大时,等离子体向外膨胀的强度增大,磁场产生的洛伦兹力束缚等离子的能力相对减弱,同时纳米金颗粒对等离子体发射光谱的增强作用被削弱,谱线强度降低,等离子体的增强因子逐渐减小后趋于稳定。通过NELIBS与磁场约束LIBS结合方式,不仅可以有效提高等离子体的发射谱线强度,改善光谱信号信噪比,而且传统LIBS方法中由于谱线强度低、背景噪声大而无法探测的微量元素可以被探测到,LIBS技术对微量元素的探测能力得到显著提高,微量元素的探测下限变得更低。NELIBS与磁场约束LIBS结合的方法具有更高的灵敏度和准确度,为激光诱导击穿光谱技术的谱线增强方法提供了新的思路,在该领域具有广阔的应用前景。     

铀元素的激光诱导击穿光谱测量分析

为促进LIBS技术在微量重金属元素检测以及核污染检测领域的应用,提高检测灵敏度和准确性,采用了激光双脉冲LIBS技术和光电双脉冲LIBS技术,分别对土壤和二氧化硅中的铀元素进行分析。首先,对激光脉冲能量、电压和采集延时等参数进行优化,提高铀元素特征谱线的强度和信噪比;然后在优化实验参数条件下,对含不同浓度铀元素的土壤样品和二氧化硅样品进行激发;选取UII 367.01 nm、 UII 454.36 nm两条铀元素的特征谱线作为分析线,通过铀元素浓度与特征谱线强度的线性关系,建立定标曲线。双脉冲激光激发条件为：激光脉冲1作为预脉冲,主要参数为1 064 nm, 90 mJ, 9.2 ns,激光脉冲2作为再加热脉冲,主要参数为355 nm, 50 mJ, 8 ns,两个脉冲的时间间隔800 ns,光谱采集相对第二个脉冲延时1μs,得到铀元素在土壤和二氧化硅两种样品中的浓度检测下限分别为572和110 mg·kg^-1,拟合优度值R²分别为0.958和0.999。在光电双脉冲激发条件下,激光脉冲作为预脉冲,主要参数为355 nm, 50 mJ, 8 ...     

A time-resolved imaging study of Cr (I) emissions from a laserplasma formed on a sample at nonnormal incidence

The effect of sample orientation on atomic emission in laser-induced breakdown spectroscopy (LIBS) was studied using time-resolved imaging and spectroscopy. The purpose of this work was to determine the effect of sampling geometry on the analytical performance of the LIBS measurement. The results obtained indicate that atoms are ejected perpendicular to the sample surface independent of the angle-of-incidence of the laser pulse. This result is consistent with previous work by others. In addition, it was found that the observed LIBS atomic emission intensities were maximum for normal laser pulse incidence, reached a minimum at 50° angle-of-incidence, and then increased as the sample was rotated to higher angles-of-incidence     

Design and construction of Q-switched Nd:YAG laser system for LIBS measurements

A passive, Q-switched pulsed, Nd:YAG laser system was designed and built, which can provide a potential compact robust laser source for portable laser induced breakdown spectroscopy systems.The developed laser system operates at 1064 nm. Each laser shot contains a train of pulses having maximum total output energy of 170 mJ. The number of pulses varies from 1–6 pulses in each laser shot depending on the pump energy. The pulse width of each pulse ranges from 20 to 30 ns. The total duration of the output pulse train is within 300 μs. The multi-pulse nature of the laser shots was employed to enhance the LIBS signal. To validate the system, LIBS measurements and analysis were performed on ancient ceramic samples collected from Al-Fustat excavation in Old Cairo. The samples belong to different Islamic periods in Egypt history. The results obtained are highly indicative that useful information can be provided to archeologists for use in restoring and repairing of precious archeological objects.