发射光谱法对早期激光诱导铝合金等离子体诊断研究

对激光诱导等离子体参数进行诊断有多种方法,其中采用发射光谱法对其诊断是一种重要的方法。文中采用Nd∶YAG固态激光器,输出波长1 064 nm红外激光与铝合金样品相互作用,深入研究了铝合金等离子体产生早期(<1 μs)谱线轮廓、谱线强度、线背比、谱线半峰宽及位移等随时间演变规律。研究表明,激光与物质相互作用早期,电子数密度非常大,电子与离子及原子之间的相互作用非常强烈,谱线的Stark展宽效应非常明显,导致多重谱线重叠在一起,随时间演变,电子数密度及电子温度的降低,多重谱线的半峰宽越来越窄且谱线轮廓对称性越来越好。MgⅠ285.212 6 nm谱线强度早期逐渐增强,大约100 ns左右谱线强度达到最大值,然后谱线强度呈逐渐减小的趋势,这是由于等离子体产生早期,电子及离子占主导地位,故早期原子谱线强度较弱,随时间演变,电子与离子之间的复合,原子数密度逐渐增加,故原子谱线逐渐增强,达到最大值之后,由于等离子体激发温度的降低,故谱线强度逐渐减弱。以NIST波长位置为参考,等离子体产生的早期谱线发生了红移,连续背景强度随时间演变呈幂函数形式急剧递减,与之相反,谱线的连续背景强度与谱线强度相比,连续背景衰减的速度更为迅速,故导致谱线信背比随时间演变呈增大趋势,本研究对等离子体早期这些现象从理论角度进行了深入探讨。     

Spectral evolution of nano-second laser interaction with Ti target in Air

Time-resolved optical emission spectroscopy has been successfully employed to investigate the evolution of plasma produced by the interaction of IR- and visible-pulsed laser beams with a titanium target in ambient air at atmospheric pressure. The characterization of the plasma-assisted pulsed laser ablation of the titanium target is discussed in this study. The emission spectrum produced by the titanium plasma in the wavelength range 200–1,000 nm has been carefully investigated for different experimental conditions. Boltzmann plots have been used in the calculation of the excitation temperature employing Ti II spectral lines at 286.23, 321.71, 325.29, 348.36, and 351.08 nm; this set of lines was tested and proved to be suitable for the measurement of the plasma temperature. The obtained temperature is in good agreement with the one obtained from Ti II spectral lines previously suggested by Hermann et al. [J. Appl. Phys. 77, 2928–2936, 1995, 22]. Moreover, the Stark broadening method has been employed for electron density measurements. In this study, the Stark width of the Ti II spectral line at 350.49 nm was used.     

Energy level offset analysis of lead atom in laser plasma

The optical emission spectra of the plasma generated by a 1064 nm laser irradiation of lead target in air were recorded and analyzed. Temporal evolvement trait of spectral lines was investigated. The Stark width and line shift were measured at different delay time and laser energies. The electron densities were determined using Stark-broadening parameters of spectral lines. The atomic energy level offset in plasma surroundings was explored by analyzing the line shift. The experimental data of Stark widths and line shifts were analyzed using the regularity of the Stark parameters’ dependence on effective ionization potential. However an inverse experimental result was found compared with the theoretical calculation. In addition, the change of the Stark widths and line shifts with the delay time and laser energies was discussed.     

样品温度对纳秒激光诱导Cu等离子体特征参数的影响

为了研究样品温度对激光诱导击穿Cu等离子体特征参数的影响,以黄铜为研究对象,在优化的实验条件下采用波长为532 nm的Nd∶YAG纳秒脉冲激光诱导激发不同温度下的块状黄铜,测量了Cu等离子体的特征谱线强度和信噪比;同时在局部热平衡条件下利用Boltzmann斜线法和Stark展宽法分析计算了不同的样品温度条件下等离子体电子温度和电子密度。实验结果表明,在激光功率为60 mW时,随着样品温度的升高,Cu的特征谱线强度和信噪比逐渐增加,样品温度为130 ℃时达到最大值,然后趋于饱和。计算表明,黄铜样品中Cu元素Cu Ⅰ 329.05 nm,Cu Ⅰ 427.51 nm,Cu Ⅰ 458.71 nm,Cu Ⅰ 510.55 nm,Cu Ⅰ 515.32 nm,Cu Ⅰ 521.82 nm, Cu Ⅰ 529.25 nm,Cu Ⅰ 578.21 nm八条谱线在130℃的相对强度相较于室温（18 ℃）下分别提高了11.55倍、4.53倍、4.72倍,3.31倍、4.47倍、4.60倍、4.25倍、4.55倍,光谱信噪比分别增大了1.35倍,2.29倍、1.76倍、2.50倍、2.45倍、2.28倍、2.50倍,2.53倍。分析认为,升高样品温度会增大样品的烧蚀质量,相对于温度较低状态增加了等离子体中样品粒子浓度,进而提高等离子体发射光谱强度。所以,适当升高样品温度能够提高谱线强度和信噪比,从而增强LIBS技术检测分析光谱微弱信号的测量精度,改善痕量元素的检测灵敏度。同时研究了改变样品温度时等离子体电子温度和电子密度的变化趋势。计算表明,当样品温度从室温上升到130 ℃的过程中,等离子体的电子温度由4 723 K上升到7 121 K时基本不再变化。这种变化规律与发射谱线强度和信噪比变化趋势一致。分析认为,这主要是由于在升高样品温度的初始阶段,激光烧蚀量增大,等离子体内能增大,从而导致等离子体电子温度升高。当激光烧蚀样品的量达到一定值后不再变化,激光能量被激发溅射出来的样品蒸发物以及尘粒的吸收、散射和反射,导致激光能量密度降低,电子温度趋于饱和,达到某种动态平衡。选用一条Cu原子谱线（324.75 nm）的Stark展宽系数计算激光等离子体的电子密度,同时研究改变样品温度时等离子电子密度的变化趋势,计算表明在样品温度为130 ℃时,Cu Ⅰ 324.75 nm对应的等离子电子密度相较于室温（18 ℃）条件下增大了1.74×1017 cm-3。该变化趋势与电子温度的变化趋势一致。适当升高样品温度使得电子密度增大,从而提高电子和原子的碰撞几率,激发更多的原子,这是增强光谱谱线强度的原因之一。由此可见,升高样品温度是一种便捷的提高LIBS检测灵敏度的有效手段。     

激光诱导煤样等离子体的表征

以脉冲Nd·YAG激光器泵浦的光学参量发生/放大器输出为激发源,获得了一种家庭用煤样品的激光诱导等离子体(laser induced plasma,LIP)发射光谱。谱线线型呈洛伦兹线型,表明等离子体加宽以Stark展宽为主。利用发射谱线的Stark展宽和强度,通过测量等离子体不同位置的发射光谱,确定了等离子体温度和电子密度的空间分布,发现二者在垂直等离子体发光火焰方向相对火焰中心对称分布,沿发光火焰方向不具有对称分布的特点。发光火焰中心的等离子体温度和电子密度最大,且发光强度较大,因此利用光谱技术测量等离子体特征量时,宜采集火焰中心的发射光谱。样品中有些元素的发射谱线线型显示,等离子体中存在很强的自吸收现象,自吸收程度和激发波长及激光能量密切相关,激发波长接近谱线中心波长时,自吸收现象最明显;随激光能量的增加,发射光谱强度增加的同时,自吸收的程度也增大。把这些现象归因于原子跃迁概率的增大及激光强度增加引起的等离子体中粒子数密度的增大。自吸收现象导致实验观测到的发射谱线强度小于LIP的真实辐射强度,对等离子体进行测量时,应选取不存在自吸收现象的谱线,以便于提高测量准确度。     

激光诱导煤粉等离子体的特性研究

本文研究了煤粉形态对于激光诱导煤粉等离子体特性的影响,以指导应用激光感生击穿光谱进行煤质测量时最佳样品形态的选择.建立了一套激光诱导击穿光谱的实验台架,对同一煤种的4个不同粒径范围的粉状样品进行激光激发与光谱分析,利用钙原子不同跃迁能级发射谱线的强度分布计算了0.3～0.5μs区间内的等离子体温度,并依据谱线Stark展宽与电子密度的关系得到了等离子体的电子密度.再对激发不同粒径煤粉样品产生的等离子体温度与电子密度进行了对比.实验证明,煤粉粒径越小,等离子体温度越高且电子密度越大,也即样品的等离子化程度越高,越有利于煤中元素的定量分析.     

激光等离子体发射谱展宽机制研究

根据激光诱导Cu等离子体的发射光谱特性,详细地讨论了谱线展宽机制;根据谱线的强度和半高宽度,计算了等离子体的电子温度和密度,给出了电子密度的时间和空间的演化规律。     

Determination of the Electron Density in an Argon Laser Plasma by Spectroscopy of the Hydrogen Hα and Hβ Lines

From measurements of the H_α and H_β spectral line profiles in a plasma, a method is developed which allows to separate the contributions of Doppler and Stark broadening. This method is superior to the deconvolution of Voigt profiles, in particular, when the lines are of low intensity. The electron density in the plasma can be calculated from the Stark broadening. An example is the low pressure (p ≈ 1 hPa) arc discharge of argon ion lasers which is characteristised by electron densities of approximately 10¹⁴ cm^?3 at heavy particle temperatures of about 10⁴ K. These plasma parameters lead to a broadening of the Balmer H_α and H_β spectral lines of hydrogen, which has a low concentration within the discharge area. The spectral lines are broadened due to the electron density dependent Stark effect and the temperature responsive Doppler effect. The results are consistent with predictions of the argon ion laser modelling.     

激光诱导击穿光谱测量偏差的物理影响因素研究

为了消除LIBS实际测量光谱谱线与标准的LIBS光谱谱线间存在的差值,提高元素测量精准度,提出了针对激光诱导击穿光谱测量偏差的物理影响因素研究。实验在相同条件下,对烧蚀孔效应和光谱波长的关系进行了测试,研究了激光诱导击穿光谱高温Mg等离子体在1.00～3.00 μs范围采样延时下的斯塔克(Stark)展宽数据,从而得出烧蚀孔效应和斯塔克延时展宽等物理因素对采集光谱造成的具体影响。研究结果及方法完全可以应用于其他激光诱导击穿光谱实验系统的误差分析,这对于提高LIBS技术的物质元素测量精准度,研究LIBS技术的最佳采样延时时间,具有重要意义。     

样品温度对纳秒激光诱导土壤等离子体辐射特性的影响

利用脉宽8 ns,波长为532 nm的Nd:YAG单脉冲纳秒激光器,在一个标准大气压下入射到土壤中(样品土壤来自蚌埠学院校园),改变样品温度,获得了不同样品温度下激光诱导击穿光谱. 通过分析光谱,得到土壤中不同特征谱线的强度和信噪比. 分别利用Boltzmann斜线法和Stark展宽法计算并分析了等离子体电子温度和电子密度随样品温度的演化规律;同时讨论了提高样品温度和激光诱导土壤等离子体辐射增强的原因. 实验结果表明,随着样品温度的升高,等离子体的谱线强度、信噪比、电子温度和电子密度会逐渐增强,并且在温度为100 °C时达到最大.     

Measurement of the Stark Broadening of Atomic Emission Lines in Non–Optically Thin Plasmas by Laser‐Induced Breakdown Spectroscopy

We propose a new method for determining the Stark broadening of atomic emission lines using laser‐induced breakdown spectroscopy. The method allows the determination of the Stark broadening in non–optically thin plasmas, through the introduction of a correction for self‐absorption. Couples of lines of the same species are considered. If one of the Stark broadenings is known, the determination of the other does not require the measurement of the electron density of the plasma. Examples are given for the application of the proposed method to the measurement of the Stark broadening of several aluminum emission lines (Al I at 308.2 nm, Al I at 394.4 nm, and Al I at 396.2 nm).     

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.     

激光烧蚀脉冲放电激发的土壤等离子体电子数密度和温度的研究

以激光烧蚀快脉冲放电激发土壤为例,研究了激光烧蚀快脉冲放电等离子体技术产生的土壤等离子体的电子数密度和温度。根据实验测得的Si原子和离子谱线的强度和萨哈玻尔兹曼方程,计算了等离子体的电子温度,并从分析Si I 250.69nm谱线的斯塔克展宽中导出了等离子体的电子数密度。与使用同样激光能量激发的激光等离子体相比,激光烧蚀快脉冲放电激发等离子体的电子数密度和温度都明显增加,与观察到的光谱信号强度是一致的。     

On the variation of spectral line widths within stark-broadened multiplets

The Stark broadening of isolated ion lines is considered in the electron impact approximation. It is shown by an elementary formulation of the theory that, under certain plasma conditions, situations may arise in complex atoms where a relatively small number of collision-induced transitions predominate in the broadening, and consequently where appreciable variations of spectral line width are obtained within multiplets. Such lines are then particularly suitable for application of the Stark-broadening mechanism as a means of studying atomic structure and collision physics.     

Spectroscopic analysis of a laser-induced NaCl–water plasma. The influence of self-absorption

A spectroscopic study of the plasma plume created by a laser beam on the surface of NaCl aqueous solution is presented. Optical emission spectra are recorded and temporally analyzed; electron number density is determined from the Stark broadening of the NI nitrogen line, and temperature is obtained from relative intensity of OI oxygen lines. The intensity of an atomic line from sodium was used to quantitate its molar percentage in the Oceanic and Mediterranean sea, and calibration curves have been constructed for concentrations ranging up to 1.5%.     

高气压微波氢等离子体发射光谱诊断

在2.45GHz,800W级的高气压微波等离子体放电系统中,通过测量不同微波功率和放电气压下氢等离子体的Balmer线系的发射光谱,从测量的谱线总展宽中卷积去掉具有高斯线形的Doppler展宽和仪器展宽得到谱线的Stark展宽,并通过Stark展宽测量氢等离子体的电子数密度和电场强度。结果表明:等离子体的电子数密度和电场强度随着放电气压的升高都是先增大后减小,随着微波功率的增加呈现逐渐增大的趋势。微波功率为800W时,气压在25kPa时电子数密度和电场强度都达到最大值,等离子体的电子数密度和内部的电场强度分别为3.55×1012cm-3及4.01kV/cm。     

Observations and analysis of resonant laser ablation of GaAs

Laser ablation of solid GaAs samples has been studied using one tunable pulsed dye laser. At relatively low laser power, enhancements of up to several hundred times have been observed in the yield of resonantly ionised Ga using laser wavelengths corresponding to the atomic transition 4² P _1/2-4² D _3/2. The influences of laser power and target geometry, on the ion yield and spectral profile, are discussed. It is argued that the resonant excitation and ionisation processes occur in the gas phase of the atoms ablated from the sample surface, and the observed asymmetric spectral profile results from laser-induced collisional processes, e.g., optical collisions, under conditions of relatively high atomic density in the interaction region. Potential applications are foreseen for resonant laser ablation in trace analysis.     

Measurement of the Stark broadening parameters of some singly ionized argon lines

Half-widths of fifteen Stark broadened argon II lines have been measured in argon plasma behind the reflected shock wave produced in an electromagnetically driven “T” tube. The plasma electron density was determined by the laser interferometry at three different wavelengths, while the plasma temperature was measured from relative intensities of A II lines. Temperatures were in the range 8,500–16,500 °K; electron densities varied from 1.82 to 3.94 · 10¹⁷ cm^?3. The measured A II linewidths are compared with theoretical and other experimental results. It is shown that a) the broadening of A II lines is in good agreement with the theory, b) line broadening increases linearly with electron density, and c) the Stark broadened lines follow the dispersion profile to the distance of at least three halfwidths from the line center.     

仪器展宽对大气压等离子体电子密度测量的影响

实验使用两台不同的单色仪,采用光谱线型法测量了大气压氩气介质阻挡放电中的电子密度.诊断结果表明,由于不同的单色仪其仪器加宽不同,仪器加宽对总的光谱线型有较大影响.通过考虑等离子体中的各种加宽机制,采用卷积和反卷积的方法对氩原子发射谱线线型进行了分析,从整个光谱线型中分离出Stark线型,排除了仪器加宽对最终诊断结果的影响.从而最终测量了大气压氩气介质阻挡放电中的电子密度.测量得到在大气压氩气介质阻挡放电中单个放电丝存在时,电子温度为10000K时,电子密度约为3.05-3.26×1021 m-3.此方法不仅可以应用在大气压介质阻挡放电中,还可以用于测量其它大气压等离子体电子密度.