Interface structure in superhard TiN-SiN nanolaminates and nanocomposites: Film growth experiments and ab initio calculations

Nanostructured materials-the subject of much of contemporary materials research-are defined by internal interfaces, the nature of which is largely unknown. Yet, the interfaces determine the properties of nanocomposites and nanolaminates. An example is nanocomposites with extreme hardness >= 70-90 GPa, which is of the order of, or higher than, diamond. The Ti-Si-N system, in particular, is attracting attention for the synthesis of such superhard materials. In this case, the nanocomposite structure consists of TiN nanocrystallites encapsulated in a fully percolated SiNx tissue phase (1 to 2 monolayers thick) that is assumed to be amorphous. Here, we show that the interfacial tissue phase can be crystalline, and even epitaxial with complex surface reconstructions. Using in situ structural analyses combined with ab initio calculations, we find that SiNx layers grow epitaxially, giving rise to strong interfacial bonding, on both TiN(001) and TiN(111) surfaces. In addition, TiN overlayers grow epitaxially on SiNx/TiN(001) bilayers in nanolaminate structures. These results provide insight into the development of design rules for new nanostructured materials.