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Iron and nickel-based perovskite oxides have proven promising for the oxygen evolution reaction (OER) in alkaline environments, as their catalytic overpotentials rival precious metal catalysts when the band alignment is tuned through substitutional doping or alloying. Here, we report the engineering of band alignment in LaFeO3/LaNiO3 (LFO/LNO) heterostructures via interfacial doping that yields greatly enhanced catalytic performance. The 0.2 eV offset (VBO) between the Fermi level in metallic LNO and the valence band in semiconducting LFO that we predict using density functional theory makes LFO a p-type semiconductor, resulting in significantly lower barriers for hole transport through LFO compared to the intrinsic material. Experimental band alignment measured with in situ x-ray photoelectron spectroscopy of epitaxial LFO/LNO heterostructures confirms these predictions, producing a measured VBO of 0.3(1) eV. Furthermore, OER catalytic measurements on these samples in the alkaline solution show an increase in catalytic current density by a factor of ∼275 compared to LFO grown on n-type Nb-doped SrTiO3. These results demonstrate the power of tuning band alignments through interfacial band engineering for improved catalytic performance of oxides. 

4d transition metal oxides have emerged as promising materials for numerous applications including high mobility electronics. SrNbO3 is one such candidate material, serving as a good donor material in interfacial oxide systems and exhibiting high electron mobility in ultrathin films. However, its synthesis is challenging due to the metastable nature of the d1 Nb4+ cation and the limitations in the delivery of refractory Nb. To date, films have been grown primarily by pulsed laser deposition (PLD), but development of a means to grow and stabilize the material via molecular beam epitaxy (MBE) would enable studies of interfacial phenomena and multilayer structures that may be challenging by PLD. To that end, SrNbO3 thin films were grown using hybrid MBE for the first time using a tris(diethylamido)(tert-butylimido) niobium precursor for Nb and an elemental Sr source on GdScO3 substrates. Varying thicknesses of insulating SrHfO3 capping layers were deposited using a hafnium tert-butoxide precursor for Hf on top of SrNbO3 films to preserve the metastable surface. Grown films were transferred in vacuo for x-ray photoelectron spectroscopy to quantify elemental composition, density of states at the Fermi energy, and Nb oxidation state. Ex situ studies by x-ray absorption near edge spectroscopy and scanning transmission electron microscopy illustrate that the SrHfO3 capping plays an important role in preserving the crystalline quality of the material and the Nb 4d1 metastable charge state under atmospheric conditions.