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Novel boron channel-based structure of boron carbide at high pressures

Boron carbide (B4C) is one of the hardest materials known to date. The extreme hardness of B4C arises from architecturally efficient B12 or B11C icosahedrons and strong inter-icosahedral B–C bonding. As an excellent material for use in ballistic armor, the mechanic limit of B4C and possible phase transitions under extreme stress conditions are of great interest. Here we systematically explored the post-icosahedral solid structures of B4C under high pressure, using an unbiased structure search method. A new structure composed of extended framework of B and zigzag chains of C is predicted to be stable above 96 GPa. The new structure was predicted to have a high Vickers hardness of 55 GPa and simultaneously to retain a metallic ground state. The exceptional mechanical properties found in this structure are attributed to strong sp3 covalent network formed under extreme pressure conditions. The predicted structure represents a new type of superhard boron carbides that form under high pressure without the presence of boron icosahedrons, which encourages experimental exploration in this direction.