Discovery of Two Polymorphs of TiP4N8 Synthesized from Binary Nitrides

TiP4N8 was obtained from the binary nitrides TiN and P3N5 upon addition of NH4F as a mineralizer at 8 GPa and 1400 degrees C. An intricate interplay of disorder and polymorphism was elucidated by in situ temperature-dependent single-crystal X-ray diffraction, STEM-HAADF, and the investigation of annealed samples. This revealed two polymorphs, which consist of dense networks of PN4 tetrahedra (degree of condensation kappa=0.5) and either augmented triangular TiN7 prisms or triangular TiN6 prisms for alpha- and beta-TiP4N8, respectively. The structures of TiP4N8 exhibit body-centered tetragonal (bct) framework topology. DFT calculations confirm the measured band gaps of alpha- and beta-TiP4N8 (1.6-1.8 eV) and predict the thermochemistry of the polymorphs in agreement with the experiments.

Automated summary

TiP4N8 was synthesized from TiN and P3N5 using NH4F as a mineralizer, resulting in two polymorphs with different structures and prism shapes. The measured band gaps were confirmed by DFT calculations, which also predicted the thermochemistry of the polymorphs.