Equilibrium and metastable phase transitions in silicon nitride at high pressure: A first-principles and experimental study

We have combined first-principles calculations and high-pressure experiments to study pressure-induced phase transitions in silicon nitride (Si 3N 4). Within the quasi-harmonic approximation, we predict that the α phase is always metastable relative to the β phase over a wide pressure-temperature range. Our lattice vibration calculations indicate that there are two significant and competing phonon-softening mechanisms in the β-Si 3N 4, while phonon softening in the α-Si 3N 4 is rather moderate. When the previously observed equilibrium high-pressure and high-temperature β → γ transition is bypassed at room temperature (RT) due to kinetic reasons, the β phase is predicted to undergo a first-order structural transformation to a denser P6̄ phase above 39 GPa. The estimated enthalpy barrier height is less than 70 meV/atom, which suggests that the transition is kinetically possible around RT. This predicted new high-pressure metastable phase should be classified as a "postphenacite" phase. Our high-pressure x-ray diffraction experiment confirms this predicted RT phase transition around 34 GPa. No similar RT phase transition is predicted for α-Si 3N 4. Furthermore, we discuss the differences in the pressure dependencies of phonon modes among the α, β, and γ phases and the consequences on their thermal properties. We attribute the phonon modes with negative Grüneisen ratios in the α and β phases as the cause of the predicted negative thermal expansion coefficients (TECs) at low temperatures in these two phases, and predict no negative TECs in the γ phase. © 2011 American Physical Society.