Development of an Atmospheric Pressure Glow Discharge Detector for Capillary Column Gas Chromatography

 The use of the change in the oscillation frequency of the current of a new atmospheric helium glow discharge for sensitive signal detection for gas chromatography is studied. The effluent of a capillary column is directed into the glow discharge cell perpendicular to the axis of the glow discharge that existed between a platinum anode and cathode. A stable discharge is obtained when several hundred volts are applied between the 0.2-mm gap between the anode and cathode. The effects of the electrode gap, discharge voltage and gas flow rate on the baseline frequency and discharge current were investigated. The chromatogram shows that the discharge current and discharge gap have a strong influence on the detector response. The discharge current shows positive peaks; however, frequency peaks are positive or negative depending on the discharge conditions. The response of the detector is in the femto-mole and pico-mole range for nonane and decane. Received August 5, 1997. Revision September 2, 1999     

Measurement of Spatial Distributions of Electron Density and Electron Temperature in Direct Current Glow Discharge by Double Langmuir Probes

The spatial distributions of electron temperature and density in a dc glow discharge that is created by a pair of planar electrodes were obtained by using double Langmuir probes. The contribution of double Langmuir probes measurement is to provide a relatively quantitative tool to identify the electron distribution behavior. Electrons gain energy from the imposed electric field, and electron temperature (T_e) rises very sharply from the cathode to the leading edge of the negative glow where T_e reaches the maximum. In this region, the number of electrons (N_e) is relatively small and does not increase much. The accelerated electrons lose energy by ionizing gas atoms, and T_e decreases rapidly from the trailing edge of the negative glow and extends to the anode. N_e was observed to increase from the cathode to the anode, which is due to the electron impact ionization and electron movement. The electron density was observed to increase with increasing discharge voltage while the electron temperature remained approximately. At 800 V and 50 mTorr argon glow discharge, Te ranged from 15 to 52 eV and Ne ranged from 6.3×10⁶/cm³ to 3.1×10⁸/cm³ in the DC glow discharge, and T_e and N_e were dependent on the axial position.     

Modeling the effect of the cathode geometry in a DC glow discharge ion source for mass spectrometry

A self-consistent, two-dimensional hybrid fluid-particle model is used to study the effect of cathode geometry on the plasma produced in an argon glow discharge for conditions typically of the commercially available glow discharge mass spectrometer system (VG9000 spectrometer and Megacell source). For a given power supply voltage and gas pressure, we show that the spatial distribution of the plasma in the discharge volume is strongly dependent on the cathode geometry. The plasma created in a discharge with a pin cathode tends to form a ring around the cathode, while the plasma in a discharge with a larger diameter, disk cathode is centered on-axis between the cathode face and the anode. The ion current arriving at the entry plane of the mass spectrometer thus depends strongly on the cathode geometry. This suggests that analytical performance can be enhanced by optimization of the cathode (sample) geometry.     

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.     

Detection of CN radicals in DC nitrogen plasma used for deposition of CNx layers

Emission spectra from a DC plasma discharge of nitrogen with a graphite cathode used for deposition of CNx layers were investigated in the visible range 350-900 nm. The spectra recorded at low and high resolution from both the negative glow and the positive column of the discharge were studied separately. All spectra are dominated by neutral and ionised N2 emission. In the positive column the violet band of the cyanogen (CN) radical was identified and analysed for vibrational structure. From a computer simulation of the rotationally resolved violet band, vibrational temperatures were derived and found to be in the intensity distribution for the nu = 0, 1 and 2 levels from thermal equilibrium. In the negative glow the strong N2+ features completely mask the spectral region of the violet band of CN. Conclusions were drawn concerning the CN formation by chemical sputtering, and the role of CN radicals in the formation of polymeric CNx layers of 1:1 = C:N stoichiometry.     

Parametric evaluation of sputtering in a planar, diode glow discharge—I. Sputtering of oxygen-free hard copper (OFHC)

A parametric evaluation of the principal factors which affect cathodic sputtering rates in glow discharge sources is performed. Employing a planar, disk cathode in the simple diode geometry, the roles of discharge voltage, current, and pressure are evaluated for the sputtering of oxygen-free hard copper (OFHC). Samples were sputtered at discharge currents of 5–70 mA over an argon pressure range of 1.5–8 torr (200–1064 Pa). In addition, the relationship between applied power and sputter weight loss is investigated. Studies indicate that the current density at the cathode surface and the discharge voltage are directly related and are keys in the determination of sputtering rates. Through factor analysis, an empirical formula is developed which is useful in quantifying sputter rates for a given set of discharge conditions.     

Comparison of the Plasma Temperature and Electron Number Density of the Pulsed Electrolyte Cathode Atmospheric Pressure Discharge and the Direct Current Solution Cathode Glow Discharge

A novel-pulsed electrolyte cathode atmospheric pressure discharge (pulsed-ECAD) plasma source driven by an alternating current (AC) power supply coupled with a high-voltage diode was generated under normal atmospheric pressure between a metal electrode and a small-sized flowing liquid cathode. The spatial distributions of the excitation, vibrational, and rotational plasma temperatures of the pulsed-ECAD were investigated. The electron excitation temperature of H T_exc(H), vibrational temperature of N₂ T_vib(N₂), and rotational temperature of OH T_rot(OH) were from 4900?±?36 to 6800?±?108 K, from 4600?±?86 to 5800?±?100 K, and from 1050?±?20 to 1140?±?10 K, respectively. The temperature characteristics of the dc solution cathode glow discharge (dc-SCGD) were also studied for the comparison with the pulsed-ECAD. The effects of operating parameters, including the discharge voltage and discharge frequency, on the plasma temperatures were investigated. The electron number densities determined in the discharge system and dc-SCGD were 3.8–18.9?×?10¹⁴?cm^–3 and 2.6?×?10¹⁴ to 17.2?×?10¹⁴?cm^–3, respectively.     

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.     

Role of powering geometries and sheath gas composition on operation characteristics and the optical emission in the liquid sampling-atmospheric pressure glow discharge

Characterization of the liquid sampling-atmospheric pressure glow discharge optical emission spectroscopy (LS-APGD-OES) source is described with regards to applications in low-flow separations such as capillary liquid chromatography and electrophoresis. Four powering modes are investigated, including the effects of the individual modes on current–voltage characteristics, analyte emission response, and temporal broadening of flow injection profiles. A concentric sheath gas is employed to stabilize the solution delivery at low liquid flow rates. Sheath gas composition (N₂ or He) effects analyte emission responses as well as gas phase rotational and excitation temperatures. The respective powering modes both measures of temperature, with the OH rotational gas temperatures ranging from ∼2100 to 3000 K and the Fe (I) excitation temperatures ranging from ∼2400 to 3600 K. Rotational temperature values increase slightly when helium is employed as a sheath gas as opposed to nitrogen, with the corresponding excitation temperatures increasing somewhat as well. Analytical response curves for Na and Hg in the various powering modes demonstrate good linearity, with the limits of detection for the analytes found to be on the order of ∼4–10 ppm for 5 μl injections; equating to absolute detection limits of between 20 and 45 ng. It is believed that the approach demonstrated here suggests further improvements that will permit applications in a wide variety of aqueous solution analyses where low-flow rates and limited volumes are encountered.     

Deposition of Silver Nanostructures on Polymer Films by Glow Discharge

Plasma Chemistry and Plasma Processing - An atmospheric pressure glow discharge generated between the solid cathode and liquid anode was applied to produce silver nanoparticles and deposition of...     

Synthesis of CdO Ultradisperse Powders Using Atmospheric Pressure Glow Discharge in Contact With Solution and the Investigation of Intermediate Products

A new plasma-solution method of the CdO ultradisperse powders synthesis was described. The atmospheric pressure direct current discharge was excited in the ambient air by applying a high direct voltage to two pointed titanium electrodes placed above liquid anode and liquid cathode in the H-shaped cell. The discharge current was 40 mA and the total input power was about 40 W. The action of the DC glow discharge on the cadmium nitrate water solution in the absence of additional reagents and without electrodes-solution contact was shown to result in the production of the solids in the liquid phase. The kinetics of particles formation was studied using turbidimetry and nephelometry methods. Powders’ chemical composition and morphology was obtained using X-ray diffraction spectroscopy (XRD), electron-dispersive X-ray spectroscopy (EDX), thermogravimetric analysis (TGA), differential-scanning calorimetry (DSC) and scanning electron microscopy (SEM). It was found that as-synthesized powders are not the pure cadmium hydroxide but the mixture of the cadmium nitrate, hydroxy nitrate and hydroxide. Some assumptions regarding the mechanisms and pathway of the chemical processes both under the plasma action on the solution and during the calcination of as-synthesized powders were discussed.     

Design and characterization of a direct current glow discharge lamp for analytical applications

This paper describes a compact, small volume direct current glow discharge lamp operating at low wattage for atomic emission spectrometric analysis and its process optimization for copper and brass solid samples. The design aspects, fundamental characteristics and analytical performance are described in detail. The discharge is observed end-on, with water-cooled cathode surface parallel to the spectroscopic entrance slit. The anode diameter is 7 mm and the minimum sample diameter required is 20 mm. The sample is located outside the lamp for easy access and interchangeability. The lamp is powered by a dc power supply capable of delivering 300 mA (max.) and 1500 V. The studies of fundamental characteristics include the current-voltage relationship and their dependence on pressure and the emission intensity of copper spectral line (324.7 nm). The studies were made in the pressure range of 2-7 mbar. Long-term stability of optical emission spectra was also recorded to be within ±0.75%. The performance of the lamp is quite linear in the pressure range 3.5-7 mbar at an applied voltage of about 450 V.     

Optogalvanic and optopotential signals in a glow discharge reveal electrode coupling effects

This study considers the coupling effect between the cathode and anode regions-the two most important regions in a glow discharge. Cathode and anode processes are tightly coupled by electron and ion coupling effects. Both electron and ion coupling effects were observed by studying excited Ar atoms in the cathode and anode regions and observing laser-induced space charge variations and the optogalvanic effect. Laser-induced space charge variations in the glow discharge were observed by the change in potential of an electrical probe. This signal, called the optopotential signal, provides useful information about the cathode and anode processes, and may become another useful spectroscopic detection method.     

Electrical Features of Radio-frequency,Atmospheric-pressure,Bare-metallic-electrode Glow Discharges

Radio-frequency (RF), atmospheric-pressure glow discharge (APGD) plasmas with bare metallic electrodes have promising prospects in the fields of plasma-aided etching, deposition, disinfection and sterilization, etc. In this paper, an induced gas discharge approach is proposed for obtaining the RF, atmospheric-pressure, γ-mode, glow discharges with pure nitrogen or air as the primary plasma-working gas using bare metallic electrodes. The discharge characteristics, including the discharge mode, the breakdown voltage and discharge voltage for sustaining α mode and/or γ mode discharges, of the RF APGD plasmas of helium, argon, nitrogen, air or their mixtures using a planar-type plasma generator are presented in this study. The uniformity (no filaments) of the discharges is confirmed by the images taken by an iCCD with a short exposure time (10 ns). The effects of different gap spacings and electrode materials on the discharge characteristics, the variations of the sheath thickness and the electron number density are also studied in this paper.     

Langmuir probe measurements of axial variation of plasma parameters in 27.1 MHz rf oxygen planar discharges

Langmuir probe studies have been performed on rf (27.1 MHz) discharges in O₂ under planar reactor conditions to determine the axial variation of the plasma parameters (positive ion density, electron temperature, and dc space potential) as a function of pressure (20–220 Pa) and power (10–150 W) or current (0.1–2 A). By monitoring the second derivative of the I–V probe characteristics, the suppression of the rf component in the probe circuit can be optimized. Referring to this problem, numerical studies provide relations for the determination of the residual rf component as well as of the dc component of the plasma potential at incomplete rf compensation. The positive ion density is obtained from the ion saturation currents. Here the effect of collisions between ions and neutral particles within the probe sheath (for p> 100 Pa) is considered. The electron energy distribution function is found to be of the Maxwellian type for all discharge conditions investigated here. If the pressure and the power exceed critical values, the axial charge carrier distribution is characterized by a valley formation in the bulk plasma center. This fact demonstrates that secondary electron emission due to ion impact on the electrode surfaces and following ionization by these electrons near the sheaths in front of the electrodes are significant processes for sustaining the discharge. At low pressures (p60 Pa) the dc plasma potential was found to be identical with the half-peak maintaining voltage of the discharge, in agreement with the model idea of a symmetric rf planar discharge where the rf voltage drop across the bulk plasma can be neglected. For growing pressure, however, the plasma system moves gradually toward a situation where the V-I characteristics of the discharge are significantly controlled by processes in the bulk plasma. This transition depends on the current density.     

Anode Magnetron Enhanced DC Glow Discharge Processes for Plasma Surface Cleaning and Polymerization

The objective of this study was to examine some fundamental factors involved in the design and construction of the anode magnetron dc glow discharge processes as well as its performance in plasma cleaning and polymerization. Those advantages of anode magnetron include the capability of the magnetron to operate at low pressure, as well as decreasing the thickness of cathode dark space, i.e., the negative glow which contains a higher concentration of ions and active species was more closely to the cathode surface, which makes the plasma surface cleaning and polymerization an effective and uniform processes. The deposition rate at a given discharge power is increased by the presence of anode magnetrons, and is also much higher relative to rf and af. The refractive index of dc plasma film at a given polymer thickness (such as TMS, 70 nm, RI: 2.4) is higher than rf, af, and cascade arc plasma (RI: 1.6–1.7).     

Analytical Potentials and Features of Atomic Emission Analysis Using Electron-Impact Excitation of Atoms in Helium under Atmospheric Pressure

A device is described for the atomic emission analysis of vaporous samples using electron-impact excitation in helium under atmospheric pressure. The device consists of a cathode atomizer with a test sample applied onto it and the anode located at 1–3 mm from the cathode. The electrons emitted by the cathode upon heating are accelerated by applying a constant voltage to the electrodes. The mechanism for the formation of a non-self-sustained gas discharge between the cathode and anode is considered and the properties of the discharge are compared to those of the known discharges used in atomic emission spectrometry. The influence of atomization temperature and helium pressure on the analytical and background signals was studied. It is shown that, under certain conditions, the analytical signal increases with helium pressure. The relative detection limits attained for a number of elements are from tenths to dozens of nanogram per liter; this is two or three orders of magnitude lower than those in inductively coupled plasma atomic emission spectrometry and of the same order of magnitude as detection limits in inductively coupled plasma mass spectrometry.     

Wachstum dünner Fluorkohlenstoffschichten auf der Anode einer Glühkathodenentladung

The polymerization of tetrafluorethylene on the anode of a hot glow discharge has been investigated. Rates of polymer deposition have been measured as a function of monomer pressure, discharge current density, and electrode surface temperature. A mechanism of polymer formation is suggested. The results are different from those obtained by polymerization of the same monomer in a glow discharge. It is concluded that negative ions have a great influence on mechanism of polymer formation. Additionally, monomer molecules adsorbed at the electrode are polymerized by electron bombardment.     

Ion kinetic energy distributions and their relationship to fundamental plasma parameters in a radio frequency glow discharge source

Studies are performed to evaluate the effect of discharge power, pressure, and sampling position on the kinetic energy of ions sampled from a radio frequency glow discharge (rf-GD) source. The average kinetic energy of ions decreases with increases in discharge power (20–40 W) and pressure (130–300 mTorr), with typical values lying in the range of 10–14 eV. Average ion kinetic energy (1KE) values increase at longer sampling distances from the cathode surface. The fundamental plasma parameters of positive ion number density (n_i) and plasma floating potential (V_f) are also measured via a Langmuir probe technique in order to investigate their relationships to the extracted ion beam characteristics. Total ion beam currents measured on a Faraday plate mounted behind the sampling cone reveal that the positive ion density and beam current track each other with respect to changes in discharge power and sampling position. The obtained IKE distributions are dominated by a broad, low energy peak extending from 0-to-20 eV with a high energy shoulder, which is indicative of rf modulation effects. Average IKEs track V_f as a function of power, pressure and sampling distance. The IKEs measured here are much lower than V_j (by −12 eV in most cases), suggesting that rf modulation effects and collisions in the anode sheath influence the observed energies.