Phenakite‐Type BeP2N4—A Possible Precursor for a New Hard Spinel‐Type Material

Abstract

BeP(2)N(4) was synthesized in a multi-anvil apparatus starting from Be(3)N(2) and P(3)N(5) at 5 GPa and 1500 degrees C. The compound crystallizes in the phenakite structure type (space group R3, no. 148) with a=1269.45(2) pm, c=834.86(2) pm, V=1165.13(4) x 10(6) pm(3) and Z=18. As isostructural and isovalence-electronic alpha-Si(3)N(4) transforms into beta-Si(3)N(4) at high pressure and temperature, we studied the phase transition of BeP(2)N(4) into the spinel structure type by using density functional theory calculations. The predicted transition pressure of 24 GPa is within the reach of today's state of the art high-pressure experimental setups. Calculations of inverse spinel-type BeP(2)N(4) revealed this polymorph to be always higher in enthalpy than either phenakite-type or spinel-type BeP(2)N(4). The predicted bulk modulus of spinel-type BeP(2)N(4) is in the range of corundum and gamma-Si(3)N(4) and about 40 GPa higher than that of phenakite-type BeP(2)N(4). This finding implies an increase in hardness in analogy to that occurring for the beta- to gamma-Si(3)N(4) transition. In hypothetical spinel-type BeP(2)N(4) the coordination number of phosphorus is increased from 4 to 6. So far only coordination numbers up to 5 have been experimentally realized (gamma-P(3)N(5)), though a sixfold coordination for P has been predicted for hypothetic delta-P(3)N(5). We believe, our findings provide a strong incentive for further high-pressure experiments in the quest for novel hard materials with yet unprecedented structural motives.