Tailoring crystal structure of high-entropy carbides in Si-based ceramic nanocomposites through precursor engineering

High-entropy carbides with tunable crystallization and growth have been demonstrated using single-source precursor derived ceramic route. The in situ nanocrystallization of high-entropy carbide phases, (Ta0.2W0.2V0.2Mo0.2Nb0.2)SiδC and (Ta0.167W0.167V0.167Mo0.167Nb0.167Si0.167)C in amorphous Si-based ceramic matrices was achieved by using polysiloxanes and polycarbosilanes as polymer precursors respectively. The results exemplify a prominent role of the architectures of the polymeric precursors in controlling the structural features of these ceramics at various length scales. In particular, it was observed that high-entropy carbides with rock salt and zinc blende crystal structures were formed when polysiloxanes and polycarbosilanes with different backbone structure were used as polymeric precursors respectively. This is attributed to the thermodynamics of nucleation of the carbidic phases in these nanocomposites. Furthermore, the precursor architecture that dictates free carbon content, influenced nanostructural features and porosity in the material. Therefore, engineering such compositionally complex phases is feasible by selecting suitable polymeric precursors.