On the use of non-hydrogenic spectral line profiles for electron density diagnostics of inductively coupled plasmas

On the basis of the analysis of the results reported in several experimental papers, we draw attention to some experimental difficulties in electron number density determination from the shapes and shifts of non-hydrogenic spectral lines in atmospheric pressure inductively coupled plasmas. Some suggestions for further work are also given.     

Characterization of laser induced plasmas by optical emission spectroscopy: A review of experiments and methods

Advances in characterization of laser induced plasmas by optical emission spectroscopy are reviewed in this article. The review is focused on the progress achieved in the determination of the physical parameters characteristic of the plasma, such as electron density, temperature and densities of atoms and ions. The experimental issues important for characterization by optical emission spectroscopy, as well as the different measurement methods are discussed. The main assumptions of the methods, namely the optical thin emission of spectral lines and the existence of local thermodynamic equilibrium in the plasma are evaluated. For dense and inhomogeneous sources of radiation such as laser induced plasmas, the characterization methods are classified in terms of the optical depth and the spatial resolution of the emission used for the measurements. The review deals firstly with optically thin spatially integrated measurements. Next, local measurements and characterization in not optically thin conditions are discussed. Two tables are included that provide reference to the works reporting measurements of electron density and temperature of laser induced plasmas generated with diverse samples.     

Parametric study of an atmospheric pressure microwave-induced plasma of the mini MIP torch — I. Two-dimensional spatially resolved electron-number density measurements

The results of spatial distribution measurements of the electron-number density, N_e, in an atmospheric pressure microwave-induced plasma in argon are presented. Electron-number density is determined from the width of the hydrogen H_β 486.13-nm line. The influence of the microwave input power in the range 80–150 W on the spatial distribution of N_e is first determined. For the selected input power of 100 W, the influence of molecular hydrogen in wet and desolvated nebulizer and support gas, and the corresponding changes in the electron density distributions are studied. The influence of potassium as a low ionization-potential element on the spatial distribution of N_e is also studied, with the result that a considerable lowering of the electron number density is detected.     

Real time measurement of the electron density of a laser generated plasma using a RC circuit

A Nd:YAG laser pulse was focused, in air or on a Cu target, between the plates of a planar charged capacitor. The plasma generates a transient redistribution of the electrical charges on the plates that can be easily measured as a voltage drop across a resistor connected to the ground plate. At the same time, the Stark broadening of the H_α spectral line (656.3 nm) obtained from the optical emission spectrum of the plasma was measured. In this work, we show that the peak of electrical signal measured on the resistor is, in the energy range of our laser (30 mJ to 220 mJ) and at time delays typical of Laser-Induced Breakdown Spectroscopy applications (500–5000 ns), univocally related to the temporal evolution of the Stark broadening of the H_α line. Therefore, after a proper calibration depending on the material and the experimental geometry, the peak of the electrical signal can be used to predict the temporal evolution of the electron density of the generated plasma.     

Optical emission spectroscopy diagnostics of inductively-driven plasmas in argon gas at low pressures

An optical emission spectroscopy method for determination of electron temperature, electron density and gas temperature is developed and applied for diagnostics of inductively-driven argon discharges in a cylindrical geometry. The discharges are maintained at frequency 27 MHz, applied power varied in the limits P = (90 – 160) W and gas pressure in the range p = (1.1 – 117.3) Pa. The method combines measurements of emission spectral line intensities and profile broadenings with a collisional-radiative model of argon plasma at low pressure. The model is employed for investigation of the plasma kinetics governing the population densities of 3p⁵4s and 3p⁵4p argon configuration levels, treated separately. In the numerical calculations the electron density and electron temperature are varied whereas the values of the third plasma parameter — the gas temperature — are involved as obtained data from the experiments. Comparison of the experimental results of the line-intensity ratios with those calculated by the model yields the values of the electron density and temperature. The dependence of the electron temperature, electron density and gas temperature on the discharge conditions is obtained and discussed in the study.     

Spectral line selection for time-resolved investigations of laser-induced plasmas by an iterative Boltzmann plot method

The aim of this work is to provide a procedure to determine time-resolved electron temperatures with minimized relative errors by the Boltzmann plot method. The applied procedure consists of two parts, a systematic theoretical spectral line selection and an iterative Boltzmann plot algorithm. After a pre-selection of an appropriate non-disturbed or overlapped set of spectral lines of a particular atomic or ionic species Boltzmann plots are generated using experimentally recorded data for every time window and laser pulse energy of interest. Spectral lines with the highest average deviations from the regression function are assumed as being not representative for the considered ensemble of spectral lines and are therefore discarded gradually until a threshold value for the coefficient of determination is exceeded. Laser-induced breakdown spectroscopy (LIBS) is applied for time-resolved and spatially integrated investigations of plasmas on 1.1750 C75 steel alloy samples with laser pulse energies ranging between 200 µJ and 2 mJ. For the specific chemical composition of these samples a selection of atomic and ionic Fe spectral lines has been carried out. In spite of the fact that only laser pulse energies in the low millijoule regime are applied the final sets of spectral lines comprise in total 61 Fe I and 12 Fe II emission lines. By applying this method electron temperatures can be determined with averaged relative errors of down to 1.8% for Fe I and 4.4% for Fe II emission lines.     

有机溶剂与水溶液引入电感耦合等离子体电子密度和电子温度轴向分布的比较

为了研究有机ICP最佳分析条件与水溶液ICP明显不同的原因,本文在不同的等离子体操作条件下测量了Hβ486.133nm Stark变宽,分别计算了有机溶剂和水溶液引入1CP轴向的n_e和Te值,并进行了比较。有机溶剂引入ICP时,在固定的功率,观测高度及载气流量下其轴向ne和Te均比用水溶液引入时低一些。有机ICP的优异分析性能只有在比水溶液ICP有较高的入射功率和较低的载气流量条件下才能展现出来。     

小尺寸等离子体电子密度原子发射光谱诊断

发射光谱法诊断技术作为一种"非接触式诊断技术",其响应时间快,分辨率高,可以满足小尺寸等离子体电子密度诊断的要求。本文综述了H谱线Stark展宽法、非H谱线Stark展宽法和Saha方程法测量电子密度的原理及近年来在小尺寸等离子体的电子密度诊断中的应用。     

Measurement of Stark broadening of Mn I and Mn II spectral lines in plasmas used for Laser-Induced Breakdown Spectroscopy

We present measurements of the Stark broadening of several Mn lines in the conditions of typical laser-induced plasmas. Single-and double-pulse Laser-Induced Breakdown spectroscopy (LIBS) configurations are studied on a series of Fe–Mn alloy samples with Mn concentration ranging from 6% to 30%. The effects of self-absorption on the measured line broadenings are discussed in detail. In particular, the experimental results evidence that self-absorption is much higher in laser-induced plasmas generated with double pulses, compared to the case of single pulse. After measurement of the electron density, the Stark coefficients of several neutral and ionic Mn lines are derived through the measure of the broadening in conditions of optically thin plasma. The results obtained for singly ionized Mn lines are compared with the theoretical and experimental data present in the literature. For the first time, experimental measurements of the Stark coefficient for several neutral Mn lines are also presented.     

Thomson scattering on argon surfatron plasmas at intermediate pressures: Axial profiles of the electron temperature and electron density

The axial profiles of the electron density n_e and electron temperature T_e of argon surfatron plasmas in the pressure range of 6–20 mbar and microwave power between 32 and 82 W have been determined using Thomson Scattering of laser irradiation at 532 nm. For the electron density and temperature we found values in the ranges 5 × 10¹⁸ < n_e < 8 × 10¹⁹ m^− 3 and 1.1 < T_e < 2.0 eV. Due to several improvements of the setup we could reduce the errors of n_e and T_e down to 8% and 3%, respectively. It is found that n_e decreases in the direction of the wave propagation with a slope that is nearly constant. The slope depends on the pressure but not on the power. Just as predicted by theories we see that increasing the power leads to longer plasma columns. However, the plasmas are shorter than what is predicted by theories based on the assumption that for the plasma-wave interaction electron–atom collisions are of minor importance (the so-called collisionless regime). The plasma vanishes long before the critical value of the electron density is reached. In contrast to what is predicted by the positive column model it is found that T_e does not stay constant along the column, but monotonically increases with the distance from the microwave launcher. Increases of more than 50% over 30 cm were found.     

Optical emission spectroscopy of CF4+O2 plasmas using a new technique

Optical emission intensities in the sheath region are not the same as those in the plasma region. This is because not only the electron density, but also the electron temperature, is different between the two regions. In this study a Cu rod is inserted into the plasma, and the rod potential is altered from the ground potential to a negative potential with a frequency of 20 Hz. The optical emission ray comes from the sheath region when the negative potential is applied, but comes form the plasma region at the ground potential. We can immediately detect the difference of the emission intensities between the plasma and the sheath regions by a lock-in amplifier. The pre-amplifier is placed prior to the lock-in amplifier. By using this pre-amplifier the output signal of the lock-in amplifier can be adjusted to zero for any emission line. the emission spectra from a CF₄+O₂ plasma are measured. A small amount of Ar gas and/or N₂ gas is added and the output signal of the lock-in amplifier is adjusted to zero for either the Ar emission line or the N₂ emission line. In a fluorine-contained plasma the F emission intensity normalized by the Ar one has been widely used in order to obtain the F density. This validity is confirmed by the present experiment. It is also confirmed that the CO emission intensity normalized by that of N₂ is proportional to the CO density. The metastable states play an important role in the optical emission intensities of CO and N₂ molecules.     

Spatial distributions of the number densities of neutral atoms and ions for the different elements in a laser induced plasma generated with a Ni-Fe-Al alloy

Spatially-resolved emission spectroscopy, including spatial devonvolution of the spectra, has been used to determine the three-dimensional distributions of the relative number densities of neutral atoms and ions of the elements present in a laser-induced plasma generated with a Ni-Fe-Al alloy. The method is based on the precise measurement of the local electronic temperature from Saha–Boltzmann plots constructed with Fe I and Fe II lines. The plasma was generated in air at atmospheric pressure using a 1064-nm Nd:YAG laser, and the emission was detected in the time window 3.0–3.5 μs. The ionization fraction was very high (above 0.9) for the three elements in the sample, only decreasing behind the expanding plasma front. The relative number densities were obtained from the emissivities of selected elemental lines as well as the temperature. The error in this procedure was estimated, and it was found that it is largely due to the uncertainties in the transition probability values used. The spatial distributions of the total relative number densities of the three elements were shown to coincide within the error, a result which is relevant to the development of models of plasma emission used in analytical applications. The ratios of the total number densities of the elements in the plasma were compared to their concentration ratios in the sample; however, the relatively high errors in the relative number densities did not permit any definitive conclusions to be drawn about the stoichiometry of the laser ablation process.     

Characterization of laser-induced plasmas by emission spectroscopy with curve-of-growth measurements. Part I: Temporal evolution of plasma parameters and self-absorption

Laser-induced plasmas have been characterized by emission spectroscopy, including the measurement of curves of growth. The plasmas have been generated in air at atmospheric pressure using an infrared Nd:YAG laser from a set of Fe–Ni alloys with varying Fe concentrations. The procedure used provides, in addition to the apparent temperature T and electron density N_e, a parameter N′l (the atom number density for 100% concentration times the length of the plasma along the line-of-sight), relevant to obtain the self-absorption and the intensity of the emission lines. The temporal evolution of the plasma parameters has been deduced from the measurement and fitting of the curves of growth. A fast temporal decrease of N′l is obtained for ions, whereas a gradual increase takes place for neutral atoms. The temporal evolution of the line intensity in the optically thin limit and the self-absorption of neutral atom and ion lines have been obtained experimentally and calculated from the evolution of the plasma parameters. The usefulness of the curve-of-growth method in measurements with time integration, in spite of the fast variation of the plasma parameters, has been demonstrated.     

Characterization of laser-induced plasmas by emission spectroscopy with curve-of-growth measurements. Part II: Effect of the focusing distance and the pulse energy

Laser-induced plasmas generated with different focusing distances and pulse energies have been characterized by a method based in emission spectroscopy that includes the measurement and calculation of curves of growth. An infrared Nd:YAG laser is used to generated the plasmas from Fe–Ni samples placed in air at atmospheric pressure. The characterization method provides a reduced set of plasma parameters (N_e, T, N′l, αA) that describe the line emission in optically thin and optically thick conditions. For a pulse energy of 100 mJ, the plasma parameters for varying focusing distances are obtained. The apparent (population averaged) temperatures for neutral atoms and ions are shown to be different in the plasmas generated with all the focusing distances. For each pulse energy (in the range 20–100 mJ), the plasmas generated with the optimum focusing distance, which corresponds to a constant value of irradiance, have been investigated. In these conditions, simple laws have been obtained for the variation of the plasma parameters with the pulse energy E: the electron density N_e and the apparent temperature T are independent of E while linear relations with E are obtained for the parameters N′l, αA. These simple laws lead to a quadratic dependence on E of the line intensities in the optically thin limit and to a variation of the intersection concentration C_int that characterizes self-absorption as E^− 1.     

高气压氮气介质阻挡放电激发态氮的实验研究

本文通过等离子体发射光谱研究了高气压介质阻挡放电中压力对于激发态氮的影响。其中压力变化范围是0.1MPa到0.5MPa,不同能级的N_2(C~3Π_u)是典型的活性物质。实验结果显示,随着实验气压增加,等离子体主体活性物质数密度从7×10~(15)cm~(-3)降至1×10~(15)cm~(-3)。电子温度随着气压的增加从5eV降至3eV。电子数密度和气压的关系较为复杂,会受到中性分子和电子温度的影响。氮分子激发过程速率常数则随着压力增加近似线性减少,从6×10~(-16)m~3/s降至3×10~(-16)m~3/s。实验结果显示,介质阻挡放电气压增加会显著减少活性物质数量、电子温度,同时近似线性减少氮分子激发过程速率常数。     

Time-resolved spectroscopy and imaging diagnostics of single pulse and collinear double pulse laser induced plasma from a glass sample

The characterization of laser-induced plasma from a glass sample was performed in the single- and double-pulse excitation regimes. The detailed information about density distributions of excited atoms and ions in the expanding plasma was obtained by using the imaging detection system providing measurements of the spatial, temporal, and spectral plasma emission characteristics. The expansion dynamics was shown to differ strongly between two excitation regimes. The enhancement factors of the line emissions in the double-pulse mode were found to be spatial dependent and to differ for the different elements in the plasma plume. The obtained results are useful for a better understanding of the main physical processes leading to the analytical improvement achieved by the use of double-pulse laser-induced breakdown spectroscopy (LIBS).     

Diagnostics of a thermal plasma jet by optical emission spectroscopy and enthalpy probe measurements

An accurate determination of electron density, temperature, and velocity distributions is of primary interest for the characterization of steady-state thermal plasma spray jets. Our diagnostic capabilities based on optical emission spectroscopy include measurements of absolute emission coefficients and Stark broadening. In addition, enthalpy probe diagnostics has also been used for temperature and velocity measurements. Observation of large discrepancies between temperatures derived from absolute emission coefficients, Stark broadening, and from enthalpy probe measurements indicate that severe deviations from LTE (local thermal equilibrium) exist in various regimes of plasma spray jets. Nonequilibrum characterization of such turbulent thermal plasma jets suggests that diffusion of high-energy electrons into the fringes of plasma jets and deviations from chemical equilibrium due to high velocities in the core of plasma jets and entrainment of cold gas, are the main reasons for these discrepancies. The establishment of a reliable data base, taking these nonequilibrium effects into account, is a prerequisite for meaningful modeling of real plasma jets.     

Differential density matrix overlap: an index for assessment of electron correlation in atoms and molecules

Summary A new index, called the differential density matrix overlap (DDMO), is proposed for assessment of the electron correlation effects in atoms and molecules. DDMO can be easily calculated as the negative value of the correlation energy derivative with respect to the relative position of the occupied and virtual orbitals. DDMO is transparent to physical interpretation. It can serve as a tool for analyzing the accuracy of approximate electron correlation methods and the validity of the Hartree-Fock wavefunction as the zeroth-order approximation. The properties of DDMO are discussed using test calculations on 11 atoms and molecules as an example.     

Radio frequency glow discharge source with integrated voltage and current probes used for sputtering rate and emission yield measurements at insulating samples

Radio frequency glow discharge optical emission spectroscopy (RF-GD-OES) is routinely used for the chemical analysis of solid samples. Two independent electrical signals from the discharge are required for quantification. When sputtering insulating samples, the voltage over the discharge is not directly measurable. The coupling capacity of the sample is required in order to calculate the discharge voltage. A procedure is outlined where the coupling capacity is determined using an electrical measurement without discharge. The calculated time-dependent discharge voltage and current are evaluated using a plasma equivalent circuit. An insulating sample is sputtered at constant cathode voltage and current. The emission yield for an aluminium line is comparable to that of conducting reference material.