Extending ζ-factor microanalysis to boron-rich ceramics: Quantification of bulk stoichiometry and grain boundary composition

Highlights: • ζ-factor microanalysis was successfully applied to quantify boron-rich ceramics. • A full range of ζ-factors were experimentally determined and validated. • Strategies to best determine boron carbide bulk stoichiometry were compared. • Boron carbide specimens with different stoichiometries were determined. • A ζ-factor raster scan technique was used to determine grain boundary compositions. -- Abstract: Accurate quantification of light elements which produce only soft X-ray lines via X-ray energy dispersive spectrometry (XEDS) has been traditionally difficult due to poor X-ray emission and detector efficiencies at low energies and significant X-ray absorption effects. The ζ-factor microanalysis method enables one to correct for these shortcomings; however, ζ-factor microanalysis has not yet been thoroughly applied to inorganic materials which are entirely or mostly composed of light elements such as boron carbide, boron nitride, or boron suboxide. This work successfully extended ζ-factor microanalysis to boron-rich ceramics and accurately determined stoichiometries of multiple boron carbides and measured grain boundary compositions of a boron carbide mixed with additives consisting of rare-earth ions. Various strategies were employed to experimentally determine a full range of ζ-factors and measurements were validated using materials of known composition including silicon hexaboride and silicon carbide. Overall, this work has shown that XEDS is a viable technique for light element quantification in (scanning) transmission electron microscopy, in terms of both the accuracy and precision, which is comparable or superior to the complementary electron energy loss spectrometry.