Characterization of helium/argon working gas systems in a radiofrequency glow discharge atomic emission source. Part I: Optical emission, sputtering and electrical characteristics

Abstract Studies are performed to determine the influence of discharge gas composition (helium/argon working gas mixtures) on the analyte emission signal intensities, sputtering rates, and DC-bias characteristics of an analytical radiofrequency glow discharge atomic emission spectroscopy (RF-GD-AES) source. As the partial pressure of He is increased from 0 to 15 torr, increased emission intensity is observed for a range of bulk and trace elements in NIST 1250 SRM (low alloy steel), regardless of the base pressure of Ar in the source (5 and 9 torr). In contrast to increases in analyte emission intensity of up to 300%, counterindicative decreases in the sputtering rates on the order of about 30–50% are observed. The magnitude of these effects depends on both the partial pressure of helium introduced to the source and the total pressure of the He and Ar gases. Use of relative emission yield (REY) to normalize changes in emission intensity to sputtering rates indicates that excitation efficiencies increase under these conditions. Increases in average electron energy and temperature appear to control this response. Decreases in both analyte emission intensities and sputter rates occur with increasing He partial pressure when the total pressure in the cell remains fixed (11 torr in these studies). Emission yields for the fixed pressure, mixed gas plasmas decrease as the partial pressure of He (He/Ar ratio) in the RF-GD source increases. In this case, decreases in electron number densities appear to dictate the lower REYs. Measurement of DC-bias values at the sample surface provide understanding with respect to the observed changes in sputtering rates as well as suggest the origins of changes in plasma electron energetics. Use of a diamond stylus profilometer provides both the quantitative sputter rate information as well as qualitative insights into the use of mixed gas plasmas for enhanced depth profiling capabilities. The analyte emission characteristics of these mixed gas plasmas can be further understood by examining fundamental Langmuir probe data for pure He and mixed Ar/He plasmas, which are presented in the following companion paper.