Bestimmung von leichten Elementen in Silicium und Selen durch Ionenaktivierungsanalyse

Zusammenfassung Elemente mit niedriger Kernladungszahl lassen sich durch Aktivierung mit thermischen Neutronen entweder überhaupt nicht oder nur mit sehr geringer Empfindlichkeit bestimmen.In den letzten Jahren gewinnt daher die Bestrahlung mit Ionen (Protonen, Deuteronen, Tritium-, ³He- und ⁴He-Ionen) zur Aktivierungsanalyse der leichten Elemente zunehmend an Bedeutung. Zwischen Ionen- und Neutronenaktivierungen bestehen prinzipielle Unterschiede, die diskutiert werden.Aufgrund ihrer relativ geringen Reichweite in Materie eignen sich Ionen besonders zur Untersuchung von Oberflächen sowie dünnen Aufdampfschichten und Korrosionsschichten. Da die Aktivierungstiefe durch entsprechende Wahl der Versuchsparameter festgelegt werden kann, laßt sich auch die Tiefenverteilung von Fremdstoffen im Matrixmaterial untersuchen.Zur Bestimmung von Sauerstoff, Stickstoff und Kohlenstoff werden Protonen- und Deuteronenreaktionen herangezogen; aber auch Elemente wie Bor und Aluminium lassen sich dureh Ionenaktivierung erfassen. Bei einer Einschußenergie der Ionen von 3,0 MeV, einer Flußdichte von 5 A/cm² und einer Bestrahlungszeit, die der Halbwertszeit des zu aktivierenden Elementes entspricht, liegt die Bestimmungsempfindlichkeit für die genannten Elemente im Bereich von 1–100 ppb.Über die Bestimmung von Kohlenstoff in Silicium und Sauerstoff in aufgedampften Selenschichten wird berichtet.

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Determination of light elements in silicon and selenium by ion-activation analysis

Elements with low atomic number either cannot be determined at all by activation with thermal neutrons or only with very poor detection limit.In recent years, irradiation with ions (protons, deuterons, tritium ions, ³He- and ⁴He-ions) for activation analysis of the light elements has therefore gained increasing importance. There are basic differences between ion and neutron activation, which are discussed.Because of their relatively small range in matter, ions are particularly suited for analyzing surfaces as well as thin deposited films and corrosion layers. Since the activation depth can be established in advance by appropriate selection of the analysis parameters, the distribution of foreign matter in the matrix material can also be analyzed.Proton and deuteron reactions are employed to determine the presence of oxygen, nitrogen and carbon, but other elements such as boron and aluminium can also be detected by ion activation. The detection limit attained in analyzing the elements mentioned is within the range of 1 to 100 ppb with an ion bombarding energy of 3.0 MeV, a flux density of 5 A/cm² and an irradiation period which corresponds to the half-life of the element to be activated.A report is given on the determination of carbon in silicon and oxygen in thin-deposited selenium films and the results are discussed.

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Vortrag bei der Tagung Analytische Probleme der Reindarstellung von Halbleitern, Wiesbaden, 24.–25. 9. 1968.

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Herrn Prof. Dr. W. Gebauhr danken wir für viele anregende Diskussionen. Für die Mithilfe bei der Bestrahlung und Auswertung sind wir Frau K. Appler, Frl. E. Lüders und Herrn H. Pfann zu Dank verpflichtet.     

High pressure studies of isoquinoline luminescence in polymeric media

The fluorescence peak of isoquinoline increases strongly in intensity with increasing pressure in polymethylmethacrylate (PMMA) and in polyisobutylene (PIB). In polyvinylalcohol the intensity decreases as the pressure increases. In all three cases the emission peak shifts to lower energy as the pressure increases. The results are consistent with the hypothesis that the ππ* state lies higher in energy than the nπ* state in non-hydrogen bonding solvents, but that the situation is reversed in hydrogen bonding solvents.     

Matrix-isolation-FTIR spectroscopy with an integrating sphere

The use of an integrating sphere for the measurement of absorption spectra of thin films is described. The thin film (for example a rare gas matrix) is grown directly on the inside surface of the sphere. Multiple reflections inside the integrating sphere lead to significant enhancement of weak absorptions of the film, increasing the sensitivity of such measurements.     

Correlation effects on energy curves for proton transfer. The cation [H5O2]+

Potential curves for proton transfer in [H₅O₂]⁺ and for the dissociation of one OH bond in [H₃O]⁺ were calculated by both ab initio and semi-empirical LCAO MO SCF CI methods. The energy barrier of the symmetric double minimum potential in [H₅O₂]⁺ is very sensitive to electron correlation. At an OO distance of 2.74 Å it decreases from the HF value of 9.5 kcal/mole to about 7.0 kcal/mole. The results of the semi-empirical calculations agree well with the ab initio data as long as only relative effects are regarded. The partitioning of correlation energy into contributions of individual electron pairs is very similar for proton transfer in [H₅O₂]⁺ and for the dissociation of one OH bond in [H₃O]⁺. In this example the proton transfer appears as a superposition of two “contracted ionic dissociation” processes. An interpretation of the behaviour of correlation during these processes is presented.     

Ab initio calculations on the interaction of oxygen containing ligands with alkali cations. The system H2CO/Li+

Ab initio calculations on formaldehyde/Li⁺ complexes are presented. The most stable arrangement is characterized by an energy of interaction of 43.2 kcal/mole, C_2v symmetry and an oxygen—lithium distance of R_OLi = 1.77 Å. A detailed analysis of the electron density function gives proof of the electrostatic nature of the complexes H₂O/Li⁺ and H₂Co/Li⁺ and shows extensive mutual polarization. The failure of the semi-empirical method to predict the changes in electron density at the Li⁺ cation correctly is explained.