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MXenes are an emerging family of highly-conductive 2D materials which have demonstrated state-of-the-art performance in electromagnetic interference shielding, chemical sensing, and energy storage. To further improve performance, there is a need to increase MXenes’ electronic conductivity. Tailoring the MXene surface chemistry could achieve this goal, as density functional theory predicts that surface terminations strongly influence MXenes' Fermi level density of states and thereby MXenes’ electronic conductivity. Here, we directly correlate MXene surface de-functionalization with increased electronic conductivity through in situ vacuum annealing, electrical biasing, and spectroscopic analysis within the transmission electron microscope. Furthermore, we show that intercalation can induce transitions between metallic and semiconductor-like transport (transitions from a positive to negative temperature-dependence of resistance) through inter-flake effects. These findings lay the groundwork for intercalation- and termination-engineered MXenes, which promise improved electronic conductivity and could lead to the realization of semiconducting, magnetic, and topologically insulating MXenes., Two-dimensional transition metal carbides and nitrides (MXenes) have emerged as highly conductive and stable materials, of promise for electronic applications. Here, the authors use in situ electric biasing and transmission electron microscopy to investigate the effect of surface termination and intercalation on electronic properties.

We investigated the metal-insulator transition for epitaxial thin films of the perovskite CaFeO3, a material with a significant oxygen ligand hole contribution to its electronic structure. We find that biaxial tensile and compressive strain suppress the metal-insulator transition temperature. By combining hard X-ray photoelectron spectroscopy, soft X-ray absorption spectroscopy, and density functional calculations, we resolve the element-specific changes to the electronic structure across the metal-insulator transition. We demonstrate that the Fe electron valence undergoes no observable change between the metallic and insulating states, whereas the O electronic configuration undergoes significant changes. This strongly supports the bond-disproportionation model of the metal-insulator transition for CaFeO3 and highlights the importance of ligand holes in its electronic structure. By sensitively measuring the ligand hole density, however, we find that it increases by ~5-10% in the insulating state, which we ascribe to a further localization of electron charge on the Fe sites. These results provide detailed insight into the metal-insulator transition of negative charge transfer compounds and should prove instructive for understanding metal-insulator transitions in other late transition metal compounds such as the nickelates., Comment: Minor typographic changes made

Modulation and \ud δ\ud -doping strategies, in which atomically thin layers of charged dopants are precisely deposited within a heterostructure, have played enabling roles in the discovery of new physical behavior in electronic materials. Here, we demonstrate a purely structural “\ud δ\ud -doping” strategy in complex oxide heterostructures, in which atomically thin manganite layers are inserted into an isovalent manganite host, thereby modifying the local rotations of corner-connected \ud MnO\ud 6\ud octahedra. Combining scanning transmission electron microscopy, polarized neutron reflectometry, and density functional theory, we reveal how local magnetic exchange interactions are enhanced within the spatially confined regions of suppressed octahedral rotations. The combined experimental and theoretical results illustrate the potential to utilize noncharge-based approaches to “doping” in order to enhance or suppress functional properties within spatially confined regions of oxide heterostructures.

The electronic properties of LaFeO3/LaMnO3 epitaxial heterojunctions are investigated to determine the valence and conduction band offsets and the nominal Mn and Fe valence states at the interface. Studying a systematic series of (LaFeO3)n/(LaMnO3)m bilayers (m ≈ 50) epitaxially grown in the (001) orientation using molecular beam epitaxy, layer-resolved electron energy loss spectroscopy reveals a lack of significant interfacial charge transfer, with a nominal 3+ valence state observed for both Mn and Fe across the interface. Through a combination of variable angle spectroscopic ellipsometry and hard X-ray photoelectron spectroscopy, type I energy level alignments are obtained at the LaFeO3/LaMnO3 interface with positive valence and conduction band offsets of (1.20 ± 0.07) eV and (0.50.7 ± 0.3) eV, respectively, with minimal band bending. Variable temperature resistivity measurements reveal that the bilayers remain insulating and that the presence of the heterojunction does not result in a conducting interface.

We report the relationship between epitaxial strain and the crystallographic orientation of the in-phase rotation axis and A-site displacements in Pbnm-type perovskite films. Synchrotron diffraction measurements of EuFeO3 films under strain states ranging from 2% compressive to 0.9% tensile on cubic or rhombohedral substrates exhibit a combination of a-a+c- and a+a-c- rotational patterns. We compare the EuFeO3 behavior with previously reported experimental and theoretical work on strained Pbnm-type films on non-orthorhombic substrates, as well as additional measurements from LaGaO3, LaFeO3, and Eu0.7Sr0.3MnO3 films on SrTiO3. Compiling the results from various material systems reveals a general strain dependence in which compressive strain strongly favors a-a+c- and a+a-c- rotation patterns and tensile strain weakly favors a-a-c+ structures. In contrast, EuFeO3 films grown on Pbnm-type GdScO3 under 2.3% tensile strain take on a uniform a-a+c- rotation pattern imprinted from the substrate, despite strain energy considerations that favor the a-a-c+ pattern. These results point to the use of substrate imprinting as a more robust route than strain for tuning the crystallographic orientations of the octahedral rotations and A-site displacements needed to realize rotation-induced hybrid improper ferroelectricity in oxide heterostructures., Comment: submitted to PRB, comments welcomed

Reversible changes of the structural and electronic transport properties of La1/3Sr2/3FeO3-δ/Gd-doped CeO2 heterostructures arising from the manipulation of δ are presented. Thermally induced oxygen loss leads to a c-axis lattice expansion and an increase in resistivity in a La1/3Sr2/3FeO3-δ film capped with Gd-doped CeO2. In a three-terminal device where a gate bias is applied across the Gd-doped CeO2 layer to alter the La1/3Sr2/3FeO3-δ oxygen stoichiometry, the ferrite channel is shown to undergo a change in resistance of an order of magnitude using gate voltages of less than 1 V applied at 500 K. The changes in resistance remain upon cooling to room temperature, in the absence of a gate bias, suggesting solid state ionic gating of perovskite oxides as a promising platform for applications in non-volatile, multistate devices.

Since the discovery of graphene, the quest for two-dimensional (2D) materials has intensified greatly. Recently, a new family of 2D transition metal carbides and carbonitrides (MXenes) was discovered that is both conducting and hydrophilic, an uncommon combination. To date MXenes have been produced as powders, flakes, and colloidal solutions. Herein, we report on the fabrication of similar to 1 x 1 cm(2) Ti3C2 films by selective etching of Al, from sputter-deposited epitaxial Ti3AlC2 films, in aqueous HF or NH4HF2. Films that were about 19 nm thick, etched with NH4HF2, transmit similar to 90% of the light in the visible-to-infrared range and exhibit metallic conductivity down to similar to 100 K. Below 100 K, the films resistivity increases with decreasing temperature and they exhibit negative magnetoresistance-both observations consistent with a weak localization phenomenon characteristic of many 2D defective solids. This advance opens the door for the use of MXenes in electronic, photonic, and sensing applications.

Epitaxial strain is a proven route to enhancing the properties of complex oxides, however, the details of how the atomic structure accommodates strain are poorly understood due to the difficulty of measuring the oxygen positions in thin films. We present a general methodology for determining the atomic structure of strained oxide films via x-ray diffraction, which we demonstrate using LaNiO3 films. The oxygen octahedral rotations and distortions have been quantified by comparing the intensities of half-order Bragg peaks, arising from the two unit cell periodicity of the octahedral rotations, with the calculated structure factor. Combining ab initio density functional calculations with these experimental results, we determine systematically how strain modifies the atomic structure of this functional oxide., 23 pages, 11 figures

We have investigated the synthesis of SrFeO3−αFγ (α and γ ≤ 1) perovskite films using topotactic fluorination reactions utilizing poly(vinylidene fluoride) as a fluorine source. Two different fluorination methods, a spin-coating and a vapor transport approach, were performed on as-grown SrFeO2.5 films. We highlight differences in the structural, compositional, and optical properties of the oxyfluoride films obtained via the two methods, providing insight into how fluorination reactions can be used to modify electronic and optical behavior in complex oxide heterostructures.