Understanding the Underlying Field Evaporation Mechanism of Pure Water Tips in High Electrical Fields

We investigated the field evaporation process of frozen water in atom probe tomography (APT) by density functional simulations. In previous experiments, a strong tailing effect was observed for peaks caused by the molecular structure (H₂O)H⁺, in contrast to other peaks. In purely field-induced and thermally assisted evaporation simulations, we found that chains of protonated water molecules were pulled out of the dielectric surface by up to 6 Å, which are stable over a wide range of field strengths. Therefore, the resulting water clusters experience only part of the acceleration after evaporation compared to molecules evaporating directly from the surface and, thus, exhibit an energy deficit, which explains the tailing effect. Our simulations provide new insight into the complex evaporation behavior of water in high electrical fields and reveal possibilities for adapting the existing reconstruction algorithms.