A synthetic protocol was developed for obtaining a single phase of polycrystalline NaAlB14 with strongly connected intergrain boundaries. NaAlB14 has a unique crystal structure with a tunnel-like covalent framework of B that traps monovalent Na and trivalent Al ions. Owing to the atmospheric instability and volatility of Na, the synthesis of polycrystalline NaAlB14 and its physical properties have not been reported yet. This study employed a two-step process to achieve single-phase polycrystalline NaAlB14. As a first step, a mixture of Al and B with excess Al was sintered in the Na vapor atmosphere followed by HCl treatment to remove excess Al as a second step. For obtaining bulk samples with strong grain connection, vacuum or high-pressure (HP) annealing was employed. HP annealing promoted bandgap shrinkage due to the crystal strain and defect levels and suppressed intergranular resistance. As a result, the HP-annealed sample achieved superior transport properties (0.1 kΩ cm at 300 K) to the vacuum-annealed sample (260 kΩ cm). Furthermore, from the viewpoint of its crystal structure and DFT calculations, the most probable site for the defect was suggested to be the Na site.

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