Phosphorus oxynitride PON, a silica analogue: structure and compression of the cristobalite-like phase; P –T phase diagram

 The structure of the cristobalite-like polymorph of phosphorus oxynitride PON has been refined using neutron powder diffraction data. It is tetragonal, space group I&4macr;2d, Z=4. The four P–(O,N) distances are equal but the tetrahedron is compressed along c. In AX₂ or ABX₄ compounds, the tetragonal I&4macr;2d or I&4macr; structure is obtained when the average ratio of the cation to anion radius is below 1.186, whereas the tetragonal P4₁2₁2 or orthorhombic C222₁ structure is obtained at low temperatures for larger ratios. The cell parameters of this PON polymorph have been determined as a function of hydrostatic pressure by in situ angle dispersive X-ray powder diffraction in a diamond-anvil cell. Under truly hydrostatic pressure, a strong anisotropic behavior is observed with the c parameter being nearly incompressible. Very slight anisotropic stress strongly modifies the high-pressure behavior. According to the pressure-temperature conditions of treatment, three phases, cristobalite-, moganite-, and quartz-like, have been obtained by quenching experiments, and the P–T phase diagram of PON was derived. The high-pressure behavior of the α-quartz, moganite, and cristobalite-like polymorphs of PON and SiO₂ is discussed. Received: 7 August 2000 / Accepted: 21 January 2001