Cubic boron nitride (cBN) is a well known superhard material that has a wide range of industrial applications. Nanostructuring of cBN is an effective way to improve its hardness by virtue of the Hall–Petch effect—the tendency for hardness to increase with decreasing grain size1, 2. Polycrystalline cBN materials are often synthesized by using the martensitic transformation of a graphite-like BN precursor, in which high pressures and temperatures lead to puckering of the BN layers3. Such approaches have led to synthetic polycrystalline cBN having grain sizes as small as ~14 nm (refs 1, 2, 4, 5). Here we report the formation of cBN with a nanostructure dominated by fine twin domains of average thickness ~3.8 nm. This nanotwinned cBN was synthesized from specially prepared BN precursor nanoparticles possessing onion-like nested structures with intrinsically puckered BN layers and numerous stacking faults. The resulting nanotwinned cBN bulk samples are optically transparent with a striking combination of physical properties: an extremely high Vickers hardness (exceeding 100 GPa, the optimal hardness of synthetic diamond), a high oxidization temperature (~1,294 °C) and a large fracture toughness (>12 MPa m1/2, well beyond the toughness of commercial cemented tungsten carbide, ~10 MPa m1/2). We show that hardening of cBN is continuous with decreasing twin thickness down to the smallest sizes investigated, contrasting with the expected reverse Hall–Petch effect below a critical grain size or the twin thickness of ~10–15 nm found in metals and alloys.
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