The results of a three-dimensional atom probe (3DAP) analysis, on a subnanometer scale, of a ceramic/metal heterophase interface, MgO/Cu, are presented. Segregation of Ag, from the Cu (Ag) matrix, at MgO/Cu interfaces is investigated and the Gibbsian interfacial excess of silver is determined; the range is 2.33 × 1018 to 5.81 × 1018 m−2. Also, silver segregation at the same MgO/Cu interfaces is analyzed employing a new approach that utilizes a proximity histogram or proxigram.

The three-dimensional (3D) atom-probe technique produces a reconstruction of the elemental chemical identities and three-dimensional positions of atoms field evaporated from a sharply pointed metal specimen, with a local radius of curvature of less than 50 nm. The number of atoms collected can be on the order of one million, representing an analysis volume of approximately 20 nm × 20 nm × 200 nm (80,000 nm3). This large amount of data allows for the identification of microstructural features in a sample, such as grain or heterophase boundaries, if the feature density is large enough. Correlation of the measured atomic positions with these identified features results in an atom-by-atom description of the chemical environment of crystallographic defects. This article outlines a data compilation technique for the generation of composition profiles in the vicinity of interfaces in a geometrically independent way. This approach is applied to quantitative determination of interfacial segregation of silver at a MgO/Cu(Ag) heterophase interface.