Uncovering the Effects of Metal Contacts on Monolayer MoS2.

Metal contacts are a key limiter to the electronic performance of two-dimensional (2D) semiconductor devices. Here, we present a comprehensive study of contact interfaces between seven metals (Y, Sc, Ag, Al, Ti, Au, Ni, with work functions from 3.1 to 5.2 eV) and monolayer MoS2 grown by chemical vapor deposition. We evaporate thin metal films onto MoS2 and study the interfaces by Raman spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, transmission electron microscopy, and electrical characterization. We uncover that (1) ultrathin oxidized Al dopes MoS2 n-type (>2 × 1012 cm-2) without degrading its mobility, (2) Ag, Au, and Ni deposition causes varying levels of damage to MoS2 (e.g. broadening Raman E' peak from <3 to >6 cm-1), and (3) Ti, Sc, and Y react with MoS2. Reactive metals must be avoided in contacts to monolayer MoS2, but control studies reveal the reaction is mostly limited to the top layer of multilayer films. Finally, we find that (4) thin metals do not significantly strain MoS2, as confirmed by X-ray diffraction. These are important findings for metal contacts to MoS2 and broadly applicable to many other 2D semiconductors.

Surfactant-Mediated Growth and Patterning of Atomically Thin Transition Metal Dichalcogenides.

The role of additives in facilitating the growth of conventional semiconducting thin films is well-established. Apparently, their presence is also decisive in the growth of two-dimensional transition metal dichalcogenides (TMDs), yet their role remains ambiguous. In this work, we show that the use of sodium bromide enables synthesis of TMD monolayers via a surfactant-mediated growth mechanism, without introducing liquefaction of metal oxide precursors. We discovered that sodium ions provided by sodium bromide chemically passivate edges of growing molybdenum disulfide crystals, relaxing in-plane strains to suppress 3D islanding and promote monolayer growth. To exploit this growth model, molybdenum disulfide monolayers were directly grown into desired patterns using predeposited sodium bromide as a removable template. The surfactant-mediated growth not only extends the families of metal oxide precursors but also offers a way for lithography-free patterning of TMD monolayers on various surfaces to facilitate fabrication of atomically thin electronic devices.

Metal-oxygen decoordination stabilizes anion redox in Li-rich oxides.

Reversible high-voltage redox chemistry is an essential component of many electrochemical technologies, from (electro)catalysts to lithium-ion batteries. Oxygen-anion redox has garnered intense interest for such applications, particularly lithium-ion batteries, as it offers substantial redox capacity at more than 4 V versus Li/Li+ in a variety of oxide materials. However, oxidation of oxygen is almost universally correlated with irreversible local structural transformations, voltage hysteresis and voltage fade, which currently preclude its widespread use. By comprehensively studying the Li2-xIr1-ySnyO3 model system, which exhibits tunable oxidation state and structural evolution with y upon cycling, we reveal that this structure-redox coupling arises from the local stabilization of short approximately 1.8 Å metal-oxygen π bonds and approximately 1.4 Å O-O dimers during oxygen redox, which occurs in Li2-xIr1-ySnyO3 through ligand-to-metal charge transfer. Crucially, formation of these oxidized oxygen species necessitates the decoordination of oxygen to a single covalent bonding partner through formation of vacancies at neighbouring cation sites, driving cation disorder. These insights establish a point-defect explanation for why anion redox often occurs alongside local structural disordering and voltage hysteresis during cycling. Our findings offer an explanation for the unique electrochemical properties of lithium-rich layered oxides, with implications generally for the design of materials employing oxygen redox chemistry.

Evidence for Ionic Liquid Gate-Induced Metallization of Vanadium Dioxide Bars over Micron Length Scales.

It has recently been shown that the metal-insulator transition in vanadium dioxide epitaxial films can be suppressed and the material made metallic to low temperatures by ionic liquid gating due to migration of oxygen. The gating is only possible on certain crystal facets where volume channels along the VO2's rutile c-axis intersect the surface. Here, we fabricate bars with the c-axis in plane and oriented parallel to or perpendicular to the length of the bars. We show that only bars with the c-axis perpendicular to the bars, for which the volume channels are accessible from the sides of the bar, can be metallized by ionic liquid gating. Moreover, we find that bars up to at least 0.5 µm wide can be fully gated, demonstrating the possibility of the electric field induced migration of oxygen over very long distances, ∼5 times longer than previously observed.

Metallization of Epitaxial VO2 Films by Ionic Liquid Gating through Initially Insulating TiO2 Layers.

Ionic liquid gating has been shown to metallize initially insulating layers formed from several different oxide materials. Of these vanadium dioxide (VO2) is of especial interest because it itself is metallic at temperatures above its metal-insulator transition. Recent studies have shown that the mechanism of ionic liquid gated induced metallization is entirely distinct from that of the thermally driven metal-insulator transition and is derived from oxygen migration through volume channels along the (001) direction of the rutile structure of VO2. Here we show that it is possible to metallize the entire volume of 10 nm thick layers of VO2 buried under layers of rutile titanium dioxide (TiO2) up to 10 nm thick. Key to this process is the alignment of volume channels in the respective oxide layers, which have the same rutile structure with clamped in-plane lattice constants. The metallization of the VO2 layers is accompanied by large structural expansions of up to ∼6.5% in the out-of-plane direction, but the structure of the TiO2 layer is hardly affected by gating. The TiO2 layers become weakly conducting during the gating process, but in contrast to the VO2 layers, the conductivity disappears on exposure to air. Indeed, even after air exposure, X-ray photoelectron spectroscopy studies show that the VO2 films have a reduced oxygen content after metallization. Ionic liquid gating of the VO2 films through initially insulating TiO2 layers is not consistent with conventional models that have assumed the gate induced carriers are of electrostatic origin.

Facet-Independent Electric-Field-Induced Volume Metallization of Tungsten Trioxide Films.

Reversible metallization of band and Mott insulators by ionic-liquid gating is accompanied by significant structural changes. A change in conductivity of seven orders of magnitude at room temperature is found in epitaxial films of WO3 with an associated monoclinic-to-cubic structural reorganization. The migration of oxygen ions along open volume channels is the underlying mechanism.

Giant reversible, facet-dependent, structural changes in a correlated-electron insulator induced by ionic liquid gating.

The use of electric fields to alter the conductivity of correlated electron oxides is a powerful tool to probe their fundamental nature as well as for the possibility of developing novel electronic devices. Vanadium dioxide (VO2) is an archetypical correlated electron system that displays a temperature-controlled insulating to metal phase transition near room temperature. Recently, ionic liquid gating, which allows for very high electric fields, has been shown to induce a metallic state to low temperatures in the insulating phase of epitaxially grown thin films of VO2. Surprisingly, the entire film becomes electrically conducting. Here, we show, from in situ synchrotron X-ray diffraction and absorption experiments, that the whole film undergoes giant, structural changes on gating in which the lattice expands by up to ∼3% near room temperature, in contrast to the 10 times smaller (∼0.3%) contraction when the system is thermally metallized. Remarkably, these structural changes are fully reversible on reverse gating. Moreover, we find these structural changes and the concomitant metallization are highly dependent on the VO2 crystal facet, which we relate to the ease of electric-field-induced motion of oxygen ions along chains of edge-sharing VO6 octahedra that exist along the (rutile) c axis.