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Paper des Monats
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Eingeladener Vortrag
- nein (164)
Clear evidence of the effects caused by hydrogen, introduced in different forms in an analytical glow discharge source (GDS) operated with argon, is presented for the different matrix elements copper, stainless steel, titanium, aluminium and silicon. When hydrogen is present even in small quantities in argon, not only are there significant changes in the emission line intensities of most elements (analyte and plasma species), but also new spectral features, such as emission bands of new compounds (hydrides of sputtered sample constituents) and a continuous background in the range ~220440 nm. Moreover, the discharge current (the dependent parameter in our experiments) decreases with increasing hydrogen concentration. Different modes of hydrogen introduction, externally in gaseous form or sputtered as a sample constituent, cause very similar effects in terms of discharge current, line intensity (of analyte and plasma gas) and emission continua, which implies similar changes in the discharge processes in the two cases. The excitation of the hydrogen continuum appears to quench the population of the argon metastables (11.55 and 11.72 eV) and, consequently, other elementary processes in the plasma in which the argon metastables take part, but to a different extent for each analyte.
The influence of hydrogen contained in a sample or otherwise introduced into a glow discharge source (GDS) is here extensively experimentally presented for the case of copper as a sample by means of the addition of small quantities of molecular hydrogen (<1% relative partial pressure) to the argon carrier gas. The progressive addition of molecular hydrogen causes different intensity changes particular to the individual lines of different species such as atomic (Cu I) and ionic (Cu II) copper, and also atomic (Ar I) and ionic (Ar II) argon. Some interesting features of the emission spectrum of hydrogen such as its line, band and even continuum spectrum are observed. It was also found that the depth resolution becomes worse even at very low concentrations of hydrogen.
Low-energy BO and BO2 emission from H2BO3 sputtered in a low-pressure high-frequency SNMS plasma
(1999)
Background corrected secondary neutral energy spectra derived from Cu powder pellets with H3BO3, MgO, Al2O3, TiO2, Y2O3 and ZrO2, show energy distributions being more or less typical for collision cascades in the cases of the metal ions M+, of O+ at energies >5 eV above the ion generation potential, and of the molecules Cu2+, AlO+, TiO+, YO+ and ZrO+, whereas the larger parts of the energy distributions of BO+and BO2+exhibit a similar shape as the Ar+plasma gas ions. From this, and from the background of the low decomposition and melting temperatures of H3BO3 and B2O3, respectively, we conclude that the detected BO and BO2 molecules have been emitted with thermal energies in processes implying lower energies than collision cascades. Evidence was found that the same holds for HBO2 and H2BO2. In order to obtain relative correction factors for MO+ molecular ion intensities, electron impact ionization cross sections have been calculated for the light MO molecules using the binary-encounter Bethe (BEB) formula, and for the respective metal M atoms by means of the semiempirical Lotz formula. For the heavy MO molecules YO and ZrO, cross sections have been estimated using the Thomson formula. The comparison of corrected relative MO/M and M/Cu intensities yields evidence that thermal (H)BOx emission amounts to the same order of magnitude as B emission from collision cascades, and that this situation is comparable to the high yield of MO molecules emitted in collision cascades from oxides with high M masses. Since the normal energy window of an HF-plasma secondary neutral mass spectrometer does not accept particles with originally thermal energies, it is concluded that these findings are relevant for quantification.