Spectroscopic investigations of glow discharges and the emissions of nonmetallic elements in the argon inductively coupled plasma.

Abstract

Spectroscopic investigations have been carried out on hollow cathode discharges adapted from laser technology for use as a spectroscopic light source and the argon inductively coupled plasma (ICP) as an excitation source for nonmetal emission. High and low voltage aluminum and copper hollow cathode discharges were studied as a source of ionic and resonant atomic metal emission. The high voltage versions achieve strongly positive current-voltage behavior through utilization of the obstructed discharge phenomenon. The current-pressure-intensity-voltage relationships for low and high voltage copper hollow cathode discharges were studied with the inert gases He, Ne, Ar, Kr, and Xe. The intensity for copper resonant atomic emission with the fill gases Ar, Kr, and Xe improved relative to neon in the high voltage lamp when compared to the low voltage lamp. Absorption measurements through the cathode bore show the ground state atom density to increase with the atomic weight of the fill gas at any given level of intensity, at the fill gas pressure yielding highest resonant atomic copper emission. The estimated ion/atom intensity ratio is increased with fill gases which have metastable or ionization energies greater than the excitation energy of the ion transition. A copper hollow cathode lamp incorporating a short positive column discharge in front of the cathode opening was investigated for its lineshape as measured spectroscopically and by its atomic absorption sensitivity. Incorporation of this positive column allowed higher intensities to be obtained at the same line quality as a commercial hollow cathode lamp. An enlarged cathode volume also improves the lineshape at a given intensity. Inductively coupled plasma spectra for the elements C, O, N, Cl, P, S, and Br were obtained in the vacuum ultraviolet utilizing a vacuum polychromator and SWR film. The detection limit for injected O₂ and N₂ detected electronically by the VUV emissions is 1.3 and 0.9 micrograms respectively with this system. A VUV filter photometer was utilized for oxygen and phosphorus analysis. The detection limit for injected oxygen was 1 microgram with this photometer; the detection limit for phosphorus as inorganic phosphate in aqueous solution is 10⁻³ M. The bandpass of the photometer limits its selectivity.