Anion-order driven polar interfaces at LaTiO₂N surfaces

Perovskite oxynitrides have recently attracted attention for their ability to photocatalytically split water. Compared to oxides the arrangement of anions in the material represents a further structural degree of freedom. The bulk oxynitride LaTiO2N prefers a bonding-dominated cis nitrogen arrangement, while we have previously shown that the (001) surface prefers a non-polar trans order to compensate polarity. Here we consider, using density functional theory calculations, the polar/non-polar interface that would necessarily be present between the two anion orders. We show that the Ti-terminated surface will adopt up to two trans ordered surface layers, which has a beneficial effect on the oxygen evolution efficiency. We then consider the hypothetical case of a polar cis ordered surface layer atop a non-polar trans bulk and show that similar electronic reconstructions as in the LaAlO3/SrTiO3 interface can be expected when interfaces between different anion orders are engineered in one and the same oxynitride material.