Emission characteristics of mixed gas plasmas in low-pressure glow discharges

Glow discharge optical emission spectrometry (GD-OES) with mixed plasma gases is reviewed. The major topic is the effect of type and content of gases added to an argon plasma on the emission characteristics as well as the excitation processes. Emphasis is placed on argon–helium, argon–oxygen, and argon–nitrogen mixed gas plasmas. Results for non-argon-matrix plasmas, such as neon–helium and nitrogen–helium mixtures, are also presented. Apart from the GD-OES, glow discharge mass spectrometry and furnace atomization plasma emission spectrometry with mixed plasma gases are also discussed.     

Emission characteristics of Grimm-style glow discharge plasmas with helium matrix plasma gas containing small amounts of nitrogen

Glow discharge plasmas with helium–(0–16%) nitrogen mixed gas were investigated as an excitation source in optical emission spectrometry. The addition increases the sputtering rate as well as the discharge current, because nitrogen molecular ions, which act as primary ions for the cathode sputtering, are produced through Penning-type ionization collisions between helium metastables and nitrogen molecules. The intensity of a silver atomic line, Ag I 338.29 nm, is monotonically elevated along with the nitrogen partial pressure added. However, the intensities of silver ionic lines, such as Ag II 243.78 nm and Ag II 224.36 nm, gave different dependence from the intensity of the atomic line: Their intensities had maximum values at a nitrogen pressure of 30 Pa when the helium pressure and the discharge voltage were kept at 2000 Pa and 1300 V. This effect is principally because the excitations of these ionic lines are caused by collisions of the second kind with helium excited species such as helium metastables and helium ion, which are quenched through collisions with nitrogen molecules added to the helium plasma. The sputtering rate could be controlled by adding small amounts of nitrogen to the helium plasma, whereas the cathode sputtering hardly occurs in the pure helium plasma.     

Emission characteristics of Grimm-style glow discharge plasmas with helium matrix plasma gas containing small amounts of nitrogen

Glow discharge plasmas with helium–(0–16%) nitrogen mixed gas were investigated as an excitation source in optical emission spectrometry. The addition increases the sputtering rate as well as the discharge current, because nitrogen molecular ions, which act as primary ions for the cathode sputtering, are produced through Penning-type ionization collisions between helium metastables and nitrogen molecules. The intensity of a silver atomic line, Ag I 338.29 nm, is monotonically elevated along with the nitrogen partial pressure added. However, the intensities of silver ionic lines, such as Ag II 243.78 nm and Ag II 224.36 nm, gave different dependence from the intensity of the atomic line: Their intensities had maximum values at a nitrogen pressure of 30 Pa when the helium pressure and the discharge voltage were kept at 2000 Pa and 1300 V. This effect is principally because the excitations of these ionic lines are caused by collisions of the second kind with helium excited species such as helium metastables and helium ion, which are quenched through collisions with nitrogen molecules added to the helium plasma. The sputtering rate could be controlled by adding small amounts of nitrogen to the helium plasma, whereas the cathode sputtering hardly occurs in the pure helium plasma.     

Emission spectroscopic studies of Grimm-type glow discharge plasma with argon-helium gas mixtures

The effect of argon/helium pressure ratios on the emission intensity of various Ar II lines is investigated for a Grimm-type glow discharge radiation source, operated with Ar-He mixtures. The relative intensities of the Ar II lines are altered significantly by mixing helium with argon. It is found that the population of the Ar⁺ excited states can be redistributed through He-Ar collisional energy transfer. The energy level of the He singlet metastable state (¹S₀,20.62 eV) is very important for these processes. If the excitation energy of Ar II lines is higher than that of the He singlet metastable, strong quenching of the Ar II line intensity is observed. However, when the excitation energy is slightly lower, some of the Ar II lines are enhanced by adding helium to the argon plasma. Energy exchanges between the Ar⁺ doublet term states and the He singlet metastable are favoured because the total spin remains unchanged before and after the He-Ar collisions. Furthermore, the helium mixing also exerts a great influence on the emission intensities of the elements sputtered from the cathode of the discharge lamp. The enhancement of Al I and Al II emission intensities at suitable Ar-He mixture ratios is discussed for when aluminum is employed as a cathode material.     

Emission characteristics of Cu in Dc voltage modulation applied glow discharge optical emission spectrometry.

In order to obtain the depth profile of a thin film, we investigated the emission characteristics of a voltage modulation glow discharge to optimize the modulation parameters (modulation voltage, offset voltage, and modulation frequency). In this study, a phase-sensitive detection method with a lock-in amplifier to the modulation technique led to a higher sensitivity and a larger signal-to-noise ratio in the emission analysis compared to the normal dc amplification method. Upon increasing the maximum voltage, the emission intensity of the Cu atomic line (CuI 239.34 nm) increased linearly at a modulation voltage of 400 V and an offset voltage of 300 V. On the other hand, the emission intensity was gradually reduced when a modulation frequency increased. It is advantageous for surface analysis that the voltage modulation technique gives a lower sputtering rate rather than the conventional dc discharge.     

Solid sample atomic absorption analysis after glow discharge sputtering

Summary The use of the Atomsource atomizer and a double-beam/two-channel AA instrument shall be described at first. It seems that this relatively new combination of sputtering chamber and atomic absorption measurement needs a long time to be applied. Both these techniques are not used normally in one laboratory by the same operators. May be the different aims to analyse solutions by AA and solids by glow discharge sputtering makes it more difficult to see the advantages. These are given, especially in the case of analysis of metals and other conducting materials, by the short time needed for sputtering and the accuracy, simplicity, and flexibility caused by AA meausurements. In addition, AA becomes available to determine elements like B, Ce, La, Nb or Zr much better than before.     

Some observations on sample sputtering in a glow discharge

Cross-sections through burn-spots on brass and gold samples produced by a glow discharge lamp have been investigated with the aid of a scanning electron microscope. These samples contain lead in the form of inclusions. Ion bombardment of the lead-rich sample in the lamp attacks these inclusions to a lesser degree than it does the matrix and cones are formed on the sample surface during sputtering. An explanation for this effect is given and the analytical aspects are discussed.     

Direct determination of arsenic in steel by glow discharge optical emission spectrometry with argon-helium mixed gas.

In glow discharge optical emission spectrometry, an argon-helium mixed gas plasma was investigated to improve the detection sensitivity of arsenic in steel samples. The emission line of arsenic was enhanced and the background intensity was simultaneously reduced when an Ar-He plasma was employed instead of an Ar plasma, which is effective for the sensitive determination of arsenic. The detection limits were calculated to be 0.009 mass% for a 700-V Ar plasma, 0.004 mass% for a 700-V Ar-He plasma, and 0.001 mass% for a 900-V Ar-He plasma.     

Particle beam sample introduction into glow discharge plasmas for speciation analysis

This paper reviews the use of the particle beam (PB) as a transport-type interface for the introduction of liquid samples into glow discharge (GD) plasmas. Emphasis is placed on the PB interface as a coupling for liquid chromatography (LC) with optical emission spectroscopy (OES) and mass spectrometry (MS) detection methods. Advantages and disadvantages of the particle beam sample introduction for LC–MS and LC–OES as well as a comparison with other interfaces (i.e. moving belt) are covered. Fundamental aspects of the particle beam such as solvent removal and analyte delivery are highlighted. Furthermore, the development of the particle beam interface is discussed regarding its potential for providing “comprehensive speciation” analysis of solution-phase samples. Specifically, the particle beam/hollow cathode–optical emission spectroscopy (PB/HC–OES) technique provides information towards metal and non-metals determinations as well molecular species identification of organic compounds, organometallics, and small biomolecules via empirical formulae determinations. Particle beam–glow discharge mass spectrometry (PB/GDMS) also provides molecular species information through fragmentation pattern analysis of plasma-produced mass spectra that are similar in structure to electron impact (EI) sources. The evolving capabilities of the PB/GD couplings deliver analytical information that is not available from any other spectrochemical source. The technique has relevance to an incredible range of analytical applications and warrants further investigation by other researchers and instrument manufacturers.     

Penetration of plasma surface modification. I. Cf4 and C2F4 glow discharge plasmas

Plasma treatment of a polymeric surface could involve at least three major mechanisms: (1) direct interaction of reactive species in the low-temperature plasma state with the surface (line of sight irradiation effect), and (2) chemical reactions of plasma-induced reactive species with the surface, and (3) reactions among reactive species and the surface (plasma polymerization). The first and the third effects are considered to be limited to the surfaces which directly contact with plasma (glow). The second effect is not limited to the surfaces that contact with plasma state but can penetrate beyond the plasma zone by diffusion. Using an assembly of fibers, of which only the top layer contacts with plasma (glow), the penetration of chemical changes caused by plasma exposure was investigated. Results indicate that the fluorination effect (incorporation of fluorine-containing moieties on the surface of polymeric substrate) penetrates through a considerable thickness of the assembly of fibers, depending on the porosity (gas permeability) of the system. Chemical reactions of plasma-induced (chemically) reactive but nonpolymerizing species with the substrate fibers seems to predominate. The direct interactions of energetic species, such as ions, electrons, and electronically excited species, with polymeric surfaces seems to play relatively minor roles in the plasma treatment investigated. The major role of plasma, in this case, seems to be creating such chemically reactive species. © 1994 John Wiley & Sons, Inc.     

Electrical characteristics of a millisecond pulsed glow discharge

A μs and ms pulsed argon glow discharge was investigated with respect to the breakdown condition (Paschen curve). Moreover, current–voltage profiles were acquired for different discharge frequencies, pulse durations, cathode–anode spacing and discharge pressures. The breakdown voltage was dependent on the cathode material (Cu, steel, Ti and Al). No severe change in the breakdown voltage was observed for a 1 ms pulse at different frequencies. However, the theoretical breakdown curve, calculated based on the Paschen equation did not fit the experimental data. The current plots for different cathode–anode spacing showed a maximum at intermediate distance (8–10 mm). These data were consistent with mass spectrometric data acquired using the same instrument in a GC-GD-TOFMS chemical speciation study.     

Comparative study on emission characteristics of d.c.- and r.f.-powered Grimm glow discharge plasmas. Use of argon spectral lines

Equivalent discharge conditions, where the intensities of the analyte are almost the same between the d.c. and the r.f. power modes, have been investigated in Grimm glow discharge emission spectrometry. The two plasmas have similar emission and sputtering characteristics, enabling the conditions to be found easily. Various emission lines of argon ion are commonly observed from the argon discharges regardless of the power modes. A method to determine the equivalent discharge conditions is suggested, based on intensity analysis of the argon ionic lines.     

Ion formation processes in the afterpeak time regime of pulsed glow discharge plasmas

The formation of ions following the termination of power in a pulsed glow discharge ion source is investigated. The populations of ionized species containing sputtered atoms M⁺, M ₂ ¹ :, and MAr⁺ are observed to maximize after the termination of discharge power. Collisions involving sputtered atoms and metastable argon atoms, Penning and associative ionization, are considered to be responsible for the formation of ions in the discharge afterpeak time regime. The domination of these ion formation processes during the afterpeak time regime is supported by the results from investigations of discharge operating parameters, metastable argon atom quenching, and ion kinetic energy distributions.     

The effect of glow discharge sputtering on the analysis of metal oxide films

The potential of radiofrequency glow discharge optical emission spectrometry (rf-GD-OES) for the quantification and the solid-state speciation of metal oxide films has been investigated in this work. Two types of oxide coatings, an iron oxide film deposited on silicon and a chromate conversion coating (CCC), were studied at 700 Pa of pressure and 30 W of forward power. The metal to oxygen ratios in the quantitative depth profiles (Fe/O and Cr/O, respectively) were used to evaluate the oxidation states of iron and chromium in the oxide films, demonstrating the capability of GD-OES technique for depth-resolved solid-state speciation. Furthermore, the effect of glow discharge sputtering on the samples surface in terms of modifications in the surface morphology and species transformations, were investigated by using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The iron and chromium oxidation states were carefully studied by XPS at the original samples surface and at the bottom of GD craters, and a systematic reduction of metal elements was observed after rf-GD-OES analysis. In the case of thin oxide films, preferential sputtering can be considered as a critical factor since oxygen atoms can be preferentially sputtered, leaving a metal-enriched surface and, therefore, promoting the reduction of metal elements. In the present study preferential sputtering was found to be sample dependent, changing the proportion of the metal reduction in the oxide film with its composition. Additionally, alternative sputter-depth-profiling techniques such as secondary ion mass spectrometry (SIMS), femtosecond laser ablation (fs-LA), and XPS ion gun were used for the analysis of the CCC in order to evaluate the reduction of Cr⁶⁺ to Cr³⁺ depending on the sputtering mechanism.     

Emission spectral characteristics of Cu,Ag, Zn,and Cd neutral atoms in a glow discharge

Detailed spectra highlighting the neutral atom emission characteristics (i.e. I lines) for Cu, Zn, Ag and Cd in a glow discharge device are presented in this study. A particular focus is the presentation of spectra that document the many high excitation energy neutral atom lines that are observed in these spectra. For Cu, several spectral lines originating from levels close to the ionization potential of copper are observed including lines from the so-called autoionizing levels which are actually just above the ionization potential for copper. Generally similar results are seen for Ag, Zn and Cd, including the observation of many high excitation energy neutral atom lines of Zn originating from the upper levels on the triplet side of the energy level diagram. The spectral data point to ion–electron recombination processes followed by stepwise de-excitation and radiative decay as a key mechanism in setting the spectral character of neutral atom emission in a glow discharge device. Unambiguous identification of spectral lines for specific transitions was facilitated by the acquisition of all spectral data utilizing a UV–visible Fourier transform spectrometer. This spectrometer provided complete and continuous coverage of the spectral region from 200 to 650 nm and allowed spectral lines to be identified with an accuracy of 1–2 pm.     

Emission spectral analysis with the glow discharge source and a resonance detector

A Grimm-type glow discharge lamp was found to have emission lines which are narrow enough to allow the advantageous use of resonance detection. Design of a cathodic sputtering cell which has an exchangeable cathode is described. The fluorescence signal from this lamp was detected electronically by either a synchronous (lock-in) detection system or a dual-gated integration (boxcar) system. It was found that the dual-gated system improved detection limits by a factor of 50 over the synchronous detection system. Calibration curves for copper in aluminium and silver in gold were found to be linear from the detection limit (about 1 ppm for both elements) up to approximately 20% in the case of copper in aluminium, and 5% silver in gold. Reproducibility of signal measurements was 1%.     

Comparative studies on excitation of nickel ionic lines between argon and krypton glow discharge plasmas

The emission characteristics of nickel ionic lines in a glow discharge plasma are investigated when argon or krypton was employed as the plasma gas. Large difference in the relative intensities of nickel ionic lines which are assigned to the 3d⁸4p–3d⁸4s transition is observed between the krypton plasma and the argon plasma. Different intense Ni II lines appear in the krypton spectrum and in the argon spectrum, such as the Ni II 231.601 nm for Kr and the Ni II 230.009 nm for Ar. The excitation energy of these Ni II emission lines can give a key in considering their excitation mechanisms. The explanation for these experimental results is that charge-transfer collisions between nickel atom and the plasma gas ion play a major role in exciting the 3d⁸4p excited levels of nickel ion. The conditions for energy resonance in the charge-transfer collision determine particular energy levels having much larger population; for example, the 3d⁸4p ⁴D_7/2 level (6.39 eV) for Kr and the 3d⁸4p ⁴P_5/2 level (8.25 eV) for Ar.     

A spectroscopic study of some radio frequency mixed gas plasmas

A spectroscopic study of some radio frequency argon-methane, sulphur, phosphorus and halogen plasmas has been carried out. Their analytical utility was assessed and some temperature measurements in the argon-methane plasma carried out. A number of novel lines is reported in the argon-sulphur plasma spectrum and an excitation process in these plasmas discussed.     

Boltzmann statistical consideration on the excitation mechanism of iron atomic lines emitted from glow discharge plasmas

A Boltzmann plot for many iron atomic lines having excitation energies of 3.3–6.9 eV was investigated in glow discharge plasmas when argon or neon was employed as the plasma gas. The plot did not show a linear relationship over a wide range of the excitation energy, but showed that the emission lines having higher excitation energies largely deviated from a normal Boltzmann distribution whereas those having low excitation energies (3.3–4.3 eV) well followed it. This result would be derived from an overpopulation among the corresponding energy levels. A probable reason for this is that excitations for the high-lying excited levels would be caused predominantly through a Penning-type collision with the metastable atom of argon or neon, followed by recombination with an electron and then stepwise de-excitations which can populate the excited energy levels just below the ionization limit of iron atom. The non-thermal excitation occurred more actively in the argon plasma rather than the neon plasma, because of a difference in the number density between the argon and the neon metastables. The Boltzmann plots yields important information on the reason why lots of Fe I lines assigned to high-lying excited levels can be emitted from glow discharge plasmas.     

Control of d.c. bias current in radio-frequency glow discharge source and its emission characteristics

A novel technique to control r.f.-powered Grimm-style glow discharge plasmas is described. A new channel of d.c. current driven by the self-bias potential is opened by using a low-pass filter circuit and a load resistor; as the result, a large number of electrons can flow along the d.c. circuit channel including the plasma body from the grounded electrode to the sample electrode. This phenomenon is effective for improvement of the detection sensitivity in the optical emission spectrometry. Atomic emission lines having lower excitation energies are predominantly enhanced by a factor of 10–20. The conduction of the d.c. bias current could promote these excitations.