How to best measure atomic segregation to grain boundaries by analytical transmission electron microscopy

This study provides an overview of the recent experiments employing methods that analyse, systematically, series of analytical spectra acquired either in nanobeam mode in a transmission electron microscope or using elemental mapping in a scanning transmission electron microscope. A general framework is presented that describes how best to analyse series of such spectra to quantify the areal density of atoms contained within a very thin layer of a matrix material, as, for example, appropriate to measure grain boundary segregation. We show that a systematic quantification of spectra as a function of area size illuminated by the electron beam eliminates the large systematic errors inherent in simpler approaches based on spatial difference methods, integration of compositional profiles acquired with highly focused nanoprobes or simple repeats of such measurements. Our method has been successfully applied to study dopant segregation to inversion domain boundaries in ZnO, to quantify the thicknesses of sub-nm thin layers during epitaxial growth by molecular beam epitaxy of (In)GaAs and to prove the absence of gettering of dopants at Σ = 3{111} grain boundaries in Si, with a precision <1 atom/nm² in all these cases.