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Charge transfer or redistribution at oxide heterointerfaces is a critical phenomenon, often leading to remarkable properties such as two-dimensional electron gas and interfacial ferromagnetism. Despite studies on LaNiO₃/LaFeO₃superlattices and heterostructures, the direction and magnitude of the charge transfer remain debated, with some suggesting no charge transfer due to the high stability of Fe³⁺(3d⁵). Here, we synthesized a series of epitaxial LaNiO₃/LaFeO₃superlattices and demonstrated partial (up to ~0.5 e⁻/interface unit cell) charge transfer from Fe to Ni near the interface, supported by density functional theory simulations and spectroscopic evidence of changes in Ni and Fe oxidation states. The electron transfer from LaFeO₃to LaNiO₃and the subsequent rearrangement of the Fe 3d band create an unexpected metallic ground state within the LaFeO₃layer, strongly influencing the in-plane transport properties across the superlattice. Moreover, we establish a direct correlation between interfacial charge transfer and in-plane electrical transport properties, providing insights for designing functional oxide heterostructures with emerging properties. 

Abstract Germanium-based oxides such as rutile GeO 2 are garnering attention owing to their wide band gaps and the prospects of ambipolar doping for application in high-power devices. Here, we present the use of germanium tetraisopropoxide (GTIP), a metal-organic chemical precursor, as a source of germanium for the demonstration of hybrid molecular beam epitaxy for germanium-containing compounds. We use Sn 1- x Ge x O 2 and SrSn 1- x Ge x O 3 as model systems to demonstrate our synthesis method. A combination of high-resolution X-ray diffraction, scanning transmission electron microscopy, and X-ray photoelectron spectroscopy confirms the successful growth of epitaxial rutile Sn 1- x Ge x O 2 on TiO 2 (001) substrates up to x  = 0.54 and coherent perovskite SrSn 1- x Ge x O 3 on GdScO 3 (110) substrates up to x  = 0.16. Characterization and first-principles calculations corroborate that germanium occupies the tin site, as opposed to the strontium site. These findings confirm the viability of the GTIP precursor for the growth of germanium-containing oxides by hybrid molecular beam epitaxy, thus providing a promising route to high-quality perovskite germanate films. 

We investigate the surface electronic structure of SrTiO 3 (STO) films grown by a hybrid molecular beam epitaxy that are both stoichiometric and nonstoichiometric by means of x-ray photoelectron spectroscopy and electron energy loss spectroscopy. Increasing the fraction of the surface that is terminated with an SrO layer is correlated with a decrease in the chemical potential whereby the valence band maximum moves closer to the Fermi level, but without a significant change in the bandgap. Inasmuch as SrO-terminated STO (001) has previously been shown to act as an electron scavenger in which carriers from the bulk are trapped, we argue that the high fraction of SrO in the terminal layer is what lowers the chemical potential in Sr-rich STO. Our experimental results provide important insights into various physical phenomena that can occur on STO (001) surfaces and their effect on bulk electronic properties. 

SrTiO 3 (STO) is an incipient ferroelectric perovskite oxide for which the onset of ferroelectric order is suppressed by quantum fluctuations. This property results in a very large increase in static dielectric constant from ∼300 at room temperature to ∼20,000 at liquid He temperature in bulk single crystals. However, the low-temperature dielectric constant of epitaxial STO films is typically a few hundred to a few thousand. Here, we use all-epitaxial capacitors of the form n -STO/undoped STO/ n -STO (001) prepared by hybrid molecular beam epitaxy, to demonstrate intrinsic dielectric constants of an unstrained STO (001) film exceeding 25,000. We show that the n -STO/undoped STO interface plays a critically important role not previously considered in determining the dielectric properties that must be properly accounted for to determine the intrinsic dielectric constant. 

Water electrolysis can use renewable electricity to produce green hydrogen, a portable fuel and sustainable chemical precursor. Improving electrolyzer efficiency hinges on the activity of the oxygen evolution reaction (OER) catalyst. Earth-abundant, ABO3-type perovskite oxides offer great compositional, structural, and electronic tunability, with previous studies showing compositional substitution can increase the OER activity drastically. However, the relationship between the tailored bulk composition and that of the surface, where OER occurs, remains unclear. Here, we study the effects of electrochemical cycling on the OER activity of La 0.5 Sr 0.5 Ni 1-x Fe x O 3-δ (x = 0-0.5) epitaxial films grown by oxide molecular beam epitaxy as a model Sr-containing perovskite oxide. Electrochemical testing and surface-sensitive spectroscopic analyses show Ni segregation, which is affected by electrochemical history, along with surface amorphization, coupled with changes in OER activity. Our findings highlight the importance of surface composition and electrochemical cycling conditions in understanding OER performance on mixed metal oxide catalysts, suggesting common motifs of the active surface with high surface area systems. 

Hybrid MBE produces epitaxial SrTiO 3 free-standing nanomembranes using remote epitaxy in an adsorption-controlled manner.