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One of the observed and reported phenomena in heterogeneous interfaces of perovskite oxides is the presence of a two dimensional electron gas (2DEG). In this study, the imperfect interface that is formed between LaLuO3 and SrTiO3 was studied. It was found using x ray diffraction pole figure that LaLuO3 is deposited on SrTiO3 in a two-domain structure with alternately charged layers parallel to the surface. First-principles calculations reveal that even though the lattices of the two materials do not match, an increase of the total potential is found at the interface between the two lattices. Due to this increased potential, electrons are drawn to the interface; since the interface is not perfectly epitaxial, 2DEG is not formed and instead semicontinuous 0D metallic segments probed by scanning tunneling microscopy and spectroscopy are spread along the interface on the LaLuO3 side. [ABSTRACT FROM AUTHOR]

Molecular rectification is expected to be observed in metal-molecule-metal tunnel junctions in which the resonance levels responsible for their transport properties are spatially localized asymmetrically with respect to the leads. Yet, effects such as electrostatic screening and formation of metal induced gap states reduce the magnitude of rectification that can be realized in such junctions. Here we suggest that junctions of the form metal-molecule(s)-semimetal mitigate these interfacial effects. We report current rectification in junctions based on the semimetal bismuth (Bi) with high rectification ratios (>10 2 ) at 1.0 V using alkanethiols, molecules for which rectification has never been observed. In addition to the alleviation of screening and surface states, the efficient rectification is argued to be related to symmetry breaking of the applied bias in these junctions because of a built-in potential within the Bi lead. The significance of this built-in potential and its implications for the future and other applications are discussed.

Conventional epitaxy plays a crucial role in current state-of-the art semiconductor technology, as it provides a path for accurate control at the atomic scale of thin films and nanostructures, to be used as the building blocks in nanoelectronics, optoelectronics, sensors, etc. Four decades ago, the terms "van der Waals" (vdW) and "quasi-vdW (Q-vdW) epitaxy" were coined to explain the oriented growth of vdW layers on 2D and 3D substrates, respectively. The major difference with conventional epitaxy is the weaker interaction between the epi-layer and the epi-substrates. Indeed, research on Q-vdW epitaxial growth of transition metal dichalcogenides (TMDCs) has been intense, with oriented growth of atomically thin semiconductors on sapphire being one of the most studied systems. Nonetheless, there are some striking and not yet understood differences in the literature regarding the orientation registry between the epi-layers and epi-substrate and the interface chemistry. Here we study the growth of WS 2 via a sequential exposure of the metal and the chalcogen precursors in a metal-organic chemical vapor deposition (MOCVD) system, introducing a metal-seeding step prior to the growth. The ability to control the delivery of the precursor made it possible to study the formation of a continuous and apparently ordered WO 3 mono- or few-layer at the surface of a c -plane sapphire. Such an interfacial layer is shown to strongly influence the subsequent quasi-vdW epitaxial growth of the atomically thin semiconductor layers on sapphire. Hence, here we elucidate an epitaxial growth mechanism and demonstrate the robustness of the metal-seeding approach for the oriented formation of other TMDC layers. This work may enable the rational design of vdW and quasi-vdW epitaxial growth on different material systems.

The conversion of CO 2 and epoxides to cyclic carbonates over a silica-supported di-iron(III) complex having a reduced Robson macrocycle ligand system is shown to proceed at 1 atm and 80 °C, exclusively producing the cis -cyclohexene carbonate from cyclohexene oxide. We examine the effect of immobilization configuration to show that the complex grafted in a semirigid configuration catalytically outperforms the rigid, flexible configurations and even the homogeneous counterparts. Using the semirigid catalyst, we are able to obtain a TON of up to 800 and a TOF of up to 37 h -1 under 1 atm CO 2 . The catalyst is shown to be recyclable with only minor leaching and no change to product selectivity. We further examine a range of epoxides with varying electron-withdrawing/donating properties. This work highlights the benefit arising from the constraining effect of a solid surface, akin to the role of hydrogen bonds in enzyme catalysts, and the importance of correctly balancing it., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)