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.     

Effect of operation parameters on the sputtering and emission processes in radiofrequency glow discharge. A comparison with the direct-current mode

In this paper, a comparison of the direct current (DC) and radiofrequency (RF) operating modes in glow discharge optical emission spectrometry (GD-OES) is carried out using the same discharge chamber, based on the Marcus design, powering alternatively with DC or RF energy. The effect of discharge pressure, the DC bias voltages and the delivered power divided by the DC-bias voltage on the sputtering rates, emission intensities and emission yields achieved for conducting materials was investigated in order to characterize both discharge types. Our results show that the effect of plasma variables on sputtering rates and emission yields using a DC-GD based on the chamber described by Marcus, can be considered to follow trends similar to those of the well-known DC-Grimm source. However, if the effect of plasma variables are compared for a DC-GD and a RF-GD, both generated by the same source as designed by Marcus, the behaviour of the DC and RF operations of the source proved to have some differences. Thus, at a fixed delivered power, the sputtering rate in the DC-GD decreases noticeably with pressure while the reverse effect is observed in the RF-GD. Moreover, under selected operating conditions, using the tin emission line (Sn I 380.102 nm), lower sputtering rates and higher emission yields were observed for the RF-GD than for the DC-GD source. Extension of known theoretical expressions and concepts from analytical DC-GD to RF-GD-OES work appears rather involved and is not yet possible.     

Effect of driving frequency on the operation of a radiofrequency glow discharge emission source

Several characteristics of the r.f. glow discharge were examined to determine their dependence on driving frequency. The cathode potential exhibited a strong dependence on frequency, as would be expected, because of the capacitive nature of the discharge. As the frequency was dropped from 13 to 6 MHz there was a dramatic rise in the r.f. voltage of the discharge (with a conductive sample), attributed to a change in the mode of power coupling. The sputtering rates of a conductive sample were dramatically greater at the lower frequencies, in part due to higher energy of the sputtering ions. The emission characteristics of the source also changed as the frequency was varied from 6 to 13 MHz. At the higher operating frequencies, atomic emission peaked at a particular r.f. power level, whereas at lower frequencies the neutral-atom signal generally increased monotonically with power. The highest signal levels were found at 20 MHz, the highest frequency studied. Detection limits were determined for both conductors and insulators; in both cases they are detector-noise-limited because of the low throughput of the spectrometer. Detection limits for a conducting sample ranged from 0.1 μ g⁻¹ at 20 MHz to 20 μ g⁻¹ at 3 MHz. The emission from an insulating sample showed the same trends as those from a conducting sample but required higher r.f. power; the greatest signals were found at 6 and 13 MHz because not enough power was available from the r.f. amplifier to reach the optimum power for the 20 MHz discharge. Detection limits for elements in a Macor^® ceramic sample ranged from 30 to 110 μg g⁻¹.     

Microwave sputtering of conductors and insulators for optical emission and mass spectrometry

A microwave-powered slab-line cavity was used to excite a discharge in low pressure argon or neon and to demonstrate the sputtering of conducting and non-conducting samples by a microwave excited discharge. Both optical emission spectroscopy and mass spectrometry were used as detection systems. The dependence of the signals on gas pressure and net microwave power was investigated.     

Microwave sputtering of conductors and insulators for optical emission and mass spectrometry

A microwave-powered slab-line cavity was used to excite a discharge in low pressure argon or neon and to demonstrate the sputtering of conducting and non-conducting samples by a microwave excited discharge. Both optical emission spectroscopy and mass spectrometry were used as detection systems. The dependence of the signals on gas pressure and net microwave power was investigated.     

Radio-frequency glow discharge ion source for high resolution mass spectrometry

A radio-frequency powered glow discharge ion source has been developed for a double-focusing mass spectrometer. The sputtering and ionization of conducting, semiconducting and insulating materials have been realized using a 13.56 MHz generator to supply the discharge operating potential. The glow discharge ion source operates stably at argon pressures of 0.1–1 hPa and radio frequency powers of 10–50 W. The influence of discharge parameters and gas inlet system on sputtering rates and ion signal intensities for semi-insulating gallium arsenide wafers has been investigated.     

Electrical and optical characteristics of a radio frequency glow discharge atomic emission source with dielectric sample atomization

A parametric study has been conducted on a radio frequency powered glow discharge atomic emission spectrometry (rf-GD-AES) source to evaluate its performance in the direct analysis of non-conducting solid materials. These experiments include both the emission and electrical characterization of this system with respect to discharge power, pressure, limiting anode orifice diameter, and sample size. The rf-GD-AES source has been demonstrated to operate interchangeably between conducting and non-conducting sample materials; however, the energy dissipated within the plasma appears to be reduced with the dielectric samples, resulting in lower emission intensities and sputtering rates. The power losses have also been found to be a function of the size, or thickness, of the sample materials. Despite these limitations of the system, preliminary emission data demonstrate that the rf-GD-AES system can be successfully employed in the direct, trace analysis of non-conducting sample materials.     

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.     

Design and properties of a microwave boosted glow discharge lamp

The operation of a glow discharge lamp with integrated microwave resonator for the analysis of electrically conducting solid samples by atomic emission spectrometry is described. While the glow discharge in argon at a pressure of 300 Pa mainly serves for the production of free sample atoms by cathodic sputtering, a 40 W microwave discharge is applied for additional excitation of the ablated material. The construction of the lamp and the optimization of the working conditions are described. The intensities as well as the signal-to-background ratios of many analytical lines were found to be improved as compared to a conventional glow discharge lamp. The analytical performance is demonstrated by analysis results for steel samples. Detection limits for 13 elements in steel are between 0.05 and 1 μg/g. Because of the optically thin plasma the new lamp shows a large linear dynamic range.     

Radio frequency glow discharge optical emission spectroscopy: a new weapon in the depth profiling arsenal

While the array of analytical methods routinely applied for depth profile analysis was fairly static over the decades of the 1980s and 1990s, there appears to be an emerging technique that has a number of very positive and complementary attributes, and warrants serious consideration by the thin film community. Radio frequency glow discharge optical emission spectroscopy (rf-GD-OES) is a technique that provides depth-resolved elemental composition information on a wide variety of sample types. In a manner very much like most depth profiling methods, the rf-GD plasma utilizes an ion sputtering step to ablate sample material in a layer-by-layer fashion. Different from the more commonly applied methods, the device operates at elevated pressures [2-10 Torr Ar (266-1,330 Pa)] and has the inherent capability of sputtering electrically insulating materials directly, without any auxiliary means of charge compensation. In addition, sputtering rates on the order of 1 micro m/min provide rapid analysis, with depth resolving powers that are comparable to high-vacuum sputtering methods. Three examples of the use of the rf-GD-OES method are presented as examples of its analytical potential: (1) boron-implanted silicon wafer, (2) a barrier-type alumina film, and (3) a porous-type alumina film. It is believed that the method holds a great deal of promise as part of the arsenal of weapons in the thin films laboratory.     

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.     

Theory of relative sputtering rates in GDOES

A detailed theory of relative sputtering rates for glow discharge optical emission spectroscopy (GDOES) is presented for the first time. The theory suggests that such sputtering rates should be nearly independent of plasma conditions. This is supported by experimental results for r.f. GDOES under varying applied power or varying pressure. Relative sputtering rates are calculated for a range of cast irons, high‐alloy steels and zinc–aluminium alloys. Within measurement uncertainties, the calculated rates agree with measured relative sputtering rates. Copyright © 2003 John Wiley & Sons, Ltd.     

Microwave plasma in argon produced by a surface wave: study of the effect of pressure on the optical emission and the potentials for analysis of gaseous samples

The possibility of chemical analysis of gaseous samples by optical emission spectroscopy has been evaluated using a microwave induced plasma created by a surface wave at 210 MHz. Methane has been introduced at low concentration (1–20 ppm) in argon gas. The emission of excited CH, CN, C₂ at atmospheric pressure, was observed along the discharge and studied as a function of the methane concentration. The influence of the pressure on CH emission is presented from 10 Torr to atmospheric pressure. Contrary to usual predictions, the emission of CH bands is maximum at about 100 Torr and not at atmospheric pressure.     

Plasma Chemical and Electrical Modeling of a Dielectric Barrier Discharge in Kr–Cl2 Gas Mixtures

This paper reports the study of the Kr–Cl₂ plasma chemistry in terms of the homogenous model of a dielectric barrier discharge and for two kinds of the applied voltage excitation shape. The effect of Cl₂ concentration in the gas mixture, as well as gas pressure and power frequency on the discharge efficiency and the 222 nm photon generation, under typical experimental operating conditions, have been investigated and discussed. Calculations suggest that the overall conversion efficiency from electrical energy to ultraviolet emission in the lamp is in the range of 4.4–12 %, and it will be very affected at high chlorine percentage (>1 %) and high gas pressure (>200 Torr). A comparison between the sinusoidal and the burst excitation waveforms reveals that the burst excitation method provides an enhanced light source performance compared to the sinusoidal wave.     

Langmuir probe study of the charged particle characteristics in an analytical radio frequency-glow discharge. Roles of discharge conditions and sample conductivity

The application of a tuned Langmuir probe to the measurement of the charged particle characteristics of electron number density, ion number density, electron energy distribution function, average electron energy and electron temperature, in an analytical radio frequency (r.f.)-glow discharge is described. Studies focus on the roles of discharge operating conditions and plasma sampling position for conductive (copper) and nonconductive (Macor) samples. Based on the data obtained here, apparent differences in plasma characteristics between conductive and nonconductive samples can be reasonably explained. For example, the sputtering of conductive samples results in plasmas with obviously higher electron and ion number densities than the sputtering of nonconductive samples (e.g. n_i = 1.8 × 10¹⁰ cm⁻³ and n_e = 1.5 × 10⁹ cm⁻³ for copper, and n_i = 8 × 10⁹ cm⁻³ and n_e = 5 × 10⁸ cm⁻³ for Macor under the conditions of argon pressure = 4 Torr, r.f. power = 30 W and sampling distance = 4.5 mm). Conversely, nonconductive samples yield electrons with higher energies (average electron energies of 15 and 7.5 eV and temperatures of 6.5 and 3.5 eV respectively for the Macor and copper samples). Lower d.c. bias potentials for the case of sputtering nonconductive samples yield reduced sputtering rates and charged particle densities, though the electrons in the latter case have higher energies and thus improved excitation capabilities. The differences between r.f.- and d.c.-glow discharge optical emission spectra are also discussed relative to reported electron energy characteristics. Studies such as these will lay the ground-work for extensive evaluation of inter-matrix type standardization for r.f.-glow discharge atomic emission spectrometry.     

Optimization of an rf-powered magnetron glow discharge for the trace analysis of glasses and ceramics

A radiofrequency (rf) powered planar magnetron glow discharge ion source has been designed and coupled to a double-focusing mass spectrometer. Superposition of the electrical field of the plasma in the cathode dark space and the magnetic field obtained from a ring-shaped magnet located directly behind the sample (cathode) form the electron traps and enhance the sputtering and ionization efficiency of the ion source. In order to establish optimum conditions for the trace analysis of nonconducting materials, mass spectrometric studies have been carried out on the ion signal intensities and energy distributions of analyte and discharge gas ions depending on pressure.     

A miniature planar magnetron glow discharge source for analysis of submicroliter volume aqueous samples using atomic emission spectroscopy

A miniature planar magnetron glow discharge source with a chamber volume of 60 ml has been designed and evaluated for the analysis of less than 1 μl of aqueous samples by atomic emission spectroscopy. Limits of detection for magnesium, silver, boron, europium and copper in the presence of a magnetic field are observed to be 3 to 40 times lower than for the source without a magnetic field when the measurements are made under the compromised discharge conditions for each type of source. Emission intensity in the presence of the magnetic field is found to increase as a square function of the discharge current. The improved detection limits for the magnetically enhanced glow discharge source are attributed to the increased current density of the discharge in the presence of the magnetic field which formed a plasma ring localized above the cathode surface. An RSD in the range 15–25% is observed for these measurements.     

Optimization of an rf-powered magnetron glow discharge for the trace analysis of glasses and ceramics

A radiofrequency (rf) powered planar magnetron glow discharge ion source has been designed and coupled to a double-focusing mass spectrometer. Superposition of the electrical field of the plasma in the cathode dark space and the magnetic field obtained from a ring-shaped magnet located directly behind the sample (cathode) form the electron traps and enhance the sputtering and ionization efficiency of the ion source. In order to establish optimum conditions for the trace analysis of nonconducting materials, mass spectrometric studies have been carried out on the ion signal intensities and energy distributions of analyte and discharge gas ions depending on pressure.     

Preparation and Characterization of TiO2 Nanotube Arrays via Anodization of Titanium Films Deposited on FTO Conducting Glass at Room Temperature

Self-organized TiO₂ nanotube arrays with micro-scale length were prepared on fluorine-doped tin oxide (FTO) conducting glass in NH₄F/glycerol electrolyte by electrochemical anodization of pure titanium films deposited by radio frequency magnetron sputtering (RFMS) at room temperature. The samples were characterized by means of field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), and photoelectrochemistry methods. The results showed that Ti films prepared at the condition of Ar pressure 0.5 Pa, power 150 W, and 0.5 h at room temperature possessed the zone T model structure with good homogeneity and high denseness. When the anodization time was prolonged from 1 to 3 h at the voltage of 30 V, the pore diameter of TiO₂ nanotubes increased from 50 to 75 nm, and the length increased from 750 to 1100 nm and then gradually decreased to 800 nm, while their wall morphology changed from smooth to rough. Also with increasing the anodization voltage, the pore diameter became larger, and the remaining oxide layer reduced, which could be easily removed by ultrasonic-chemical cleaning in 0.05% (w, mass fraction) diluted HF solution. Moreover, the photocurrent response curves and electrochemical impedance spectroscopy (EIS) results indicated that UV-illumination clearly enhanced the effective separation of the electron-hole pairs and the crystallized electrodes from the annealing treatment of as-anodized electrodes at 450 °C exhibited a better photoelectrochemical performance.