An Exceptionally Narrow Band-Gap (∼4 eV) Silicate Predicted in the Cubic Perovskite Structure: BaSiO3.

The electronic structures of 35 A2+B4+O3 ternary cubic perovskite oxides, including their hypothetical chemical compositions, were calculated by a hybrid functional method with the expectation that peculiar electronic structures and unique carrier transport properties suitable for semiconductor applications would be hidden in high-symmetry cubic perovskite oxides. We found unique electronic structures of Si-based oxides (A = Mg, Ca, Sr, and Ba, and B = Si). In particular, the unreported cubic BaSiO3 has a very narrow band gap (4.1 eV) compared with conventional nontransition-metal silicates (e.g., ∼9 eV for SiO2 and the calculated value of 7.3 eV for orthorhombic BaSiO3) and a small electron effective mass (0.3m0, where m0 is the free electron rest mass). The narrow band gap is ascribed to the nonbonding state of Si 3s and the weakened Madelung potential. The existence of the predicted cubic perovskite structure of BaSiO3 was experimentally verified by applying a high pressure of 141 GPa. The present finding indicates that it could be possible to develop a new transparent oxide semiconductor of earth abundant silicates if the symmetry of its crystal structure is appropriately chosen. Cubic BaSiO3 is a candidate for high-performance oxide semiconductors if this phase can be stabilized at room temperature and ambient pressure.