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Transition-metal oxides host a wide variety of electronic phenomena that can be significantly influenced by the effective dimensionality of the system under consideration. These include charge, spin, and orbital orderings, as well as unconventional superconductivity. In this context, the Ruddlesden-Popper chromates Srn+1CrnO3n+1 emerge as a particularly intriguing series of materials. Formally, the chromium atom displays a rather special 4+ oxidation state throughout the entire series. However, the effective dimensionality changes from quasi-2D to 3D as n increases from 1 to ∞. As a result, the insulating antiferromagnetic behavior observed for n=1,2,3 transforms into itinerant antiferromagnetism with reduced transition temperature for the n=∞ end member of the series, i.e., the perovskite SrCrO3. Further, distinct orbital orderings with exotic singlet states have been predicted for these systems. However, the lack of single-crystal bulk or thin-film samples has made experimental progress difficult. Here we demonstrate the synthesis of thin films of the perovskite SrCrO3 and the associated layered chromates via oxide molecular beam epitaxy for n=1 to n=5. Our electrical transport measurements reveal a gradual evolution from a strongly insulating state in Sr2CrO4 to a metallic state in the end member SrCrO3. X-ray absorption spectroscopy measurements demonstrate a varying hybridization strength of the Cr4+ valence electrons across the series, helping to explain the trend in conduction. Density functional theory calculations further confirm the observed transport trend and identify additional distortions present in the system.

Correction to: Nature Communicationshttps://doi.org/10.1038/s41467-023-37117-4, published online 16 March 2023 In the Acknowledgements section of this article the grant number relating to NSF was incorrectly given as DMR 2045826 and should have been DMR-2045826. The original article has been corrected.

The layered square-planar nickelates, Ndn+1NinO2n+2, are an appealing system to tune the electronic properties of square-planar nickelates via dimensionality; indeed, superconductivity was recently observed in Nd6Ni5O12 thin films. Here, we investigate the role of epitaxial strain in the competing requirements for the synthesis of the n = 3 Ruddlesden-Popper compound, Nd4Ni3O10, and subsequent reduction to the square-planar phase, Nd4Ni3O8. We synthesize our highest quality Nd4Ni3O10 films under compressive strain on LaAlO3 (001), while Nd4Ni3O10 on NdGaO3 (110) exhibits tensile strain-induced rock salt faults but retains bulk-like transport properties. A high density of extended defects forms in Nd4Ni3O10 on SrTiO3 (001). Films reduced on LaAlO3 become insulating and form compressive strain-induced c-axis canting defects, while Nd4Ni3O8 films on NdGaO3 are metallic. This work provides a pathway to the synthesis of Ndn+1NinO2n+2 thin films and sets limits on the ability to strain engineer these compounds via epitaxy.

The rare-earth nickelates possess a diverse set of collective phenomena including metal-to-insulator transitions, magnetic phase transitions, and upon chemical reduction, superconductivity. Here, we demonstrate epitaxial stabilization of layered nickelates in the Ruddlesden-Popper form Ndn+1NinO3n+1 using molecular beam epitaxy. By optimizing the stoichiometry of the parent perovskite NdNiO3, we can reproducibly synthesize the n=1-5 member compounds. X-ray absorption spectroscopy at the O K and Ni L edges indicate systematic changes in both the nickel-oxygen hybridization level and nominal nickel filling from 3d8 to 3d7 as we move across the series from n=1 to ∞. The n=3-5 compounds exhibit weakly hysteretic metal-to-insulator transitions with transition temperatures that depress with increasing order toward NdNiO3 (n=∞).

The oxidation- and air-stability of 2D gallium-intercalated monolayer epitaxial graphene was determined using correlative microscopy. Site-specific studies including AFM, scanning electron microscope, cross section STEM-HAADF, and EELS revealed that the oxygen signal detected by XPS and AES analyses originated from oxidized surface carbon contaminants without the presence of oxygen at the 2D gallium layers. In addition, the air-stability of the 2D gallium was correlated with the presence of intact epitaxial graphene. The absence of graphene leads to oxidation of the 2D gallium in air, consequently losing the crystallinity of the epitaxial gallium layer. This study invokes the importance of correlative microscopy to better understand defects in 2D metals that have been recently recognized through the confinement heteroepitaxy. In addition, this study highlights the advantage of using high spatial resolution STEM techniques in comparison with XPS that has relatively lower resolution. [ABSTRACT FROM AUTHOR]

Novel confinement techniques facilitate the formation of non‐layered 2D materials. Here it is demonstrated that the formation and properties of 2D oxides (GaOx, InOx, SnOx) at the epitaxial graphene (EG)/silicon carbide (SiC) interface is dependent on the EG buffer layer properties prior to element intercalation. Using 2D Ga, it is demonstrated that defects in the EG buffer layer lead to Ga transforming to GaOx with non‐periodic oxygen in a crystalline Ga matrix via air oxidation at room temperature. However, crystalline monolayer GaO2 and bilayer Ga2O3 with ferroelectric wurtzite structure(FE‐WZ') can then be formed via subsequent high‐temperature O2 annealing. Furthermore, the graphene/X/SiC (X = 2D Ga or Ga2O3) junction is tunable from Ohmic to a Schottky or tunnel barrier depending on the interface species. Finally, using vertical transport measurements and electron energy loss spectroscopy analysis, the bandgap of 2D gallium oxide is identified as 6.6 ± 0.6 eV, significantly larger than that of bulk β‐Ga2O3 (≈4.8 eV), suggesting strong quantum confinement effects at the 2D limit. The study presented here is foundational for development of atomic‐scale, vertical 2D/3D heterostructure for applications requiring short transit times, such as GHz and THz devices. [ABSTRACT FROM AUTHOR]

This work is a systematic experimental and theoretical study of the in‐plane dielectric functions of 2D gallium and indium films consisting of two or three atomic metal layers confined between silicon carbide and graphene with a corresponding bonding gradient from covalent to metallic to van der Waals type. k‐space resolved free electron and bound electron contributions to the optical response are identified, with the latter pointing towards the existence of thickness dependent quantum confinement phenomena. The resonance energies in the dielectric functions and the observed epsilon near‐zero behavior in the near infrared to visible spectral range, are dependent on the number of atomic metal layers and properties of the metal involved. A model‐based spectroscopic ellipsometry approach is used to estimate the number of atomic metal layers, providing a convenient route over expensive invasive characterization techniques. A strong thickness and metal choice dependence of the light–matter interaction makes these half van der Waals 2D polar metals attractive for quantum engineered metal films, tunable (quantum‐)plasmonics and nano‐photonics. [ABSTRACT FROM AUTHOR]