Wurtzite boron nitride (w-BN) is a metastable superhard material that is a high-pressure polymorph of BN. Clarifying how the metastable high-pressure material can be stabilized at atmospheric pressure is a challenging issue of fundamental scientific importance and promising technological value. Here, we fabricate millimeter-size w-BN bulk crystals via the hexagonal-to-wurtzite phase transformation at high pressure and high temperature. By combining transmission electron microscopy and ab initio molecular dynamics simulations, we reveal a stabilization mechanism for w-BN, i.e., the metastable high-pressure phase can be stabilized by 3D networks of planar defects which are constructed by a high density of intersecting (0001) stacking faults and {10[Formula: see text]0} inversion domain boundaries. The 3D networks of planar defects segment the w-BN bulk crystal into numerous nanometer-size prismatic domains with the reverse crystallographic polarities. Our findings unambiguously demonstrate the retarding effect of crystal defects on the phase transformations of metastable materials, which is in contrast to the common knowledge that the crystal defects in materials will facilitate the occurrence of phase transformations.
Keywords: electron microscopy; metastable phase; planar defect; superhard material.