An interface between an oxide and an electrolyte gives rise to various processes as exemplified by electrostatic charge accumulation/depletion and electrochemical reactions such as intercalation/decalation under electric field. Here we directly compare typical device operations of those in electric double layer transistor geometry by adopting ${A}$-site vacant perovskite WO$_3$ epitaxial thin films as a channel material and two different electrolytes as gating agent. $\textit{In situ}$ measurements of x-ray diffraction and channel resistance performed during the gating revealed that in both the cases WO$_3$ thin film reaches a new metallic state through multiple phase transitions, accompanied by the change in out-of-plane lattice constant. Electrons are electrostatically accumulated from the interface side with an ionic liquid, while alkaline metal ions are more uniformly intercalated into the film with a polymer electrolyte. We systematically demonstrate this difference in the electrostatic and electrochemical processes, by comparing doped carrier density, lattice deformation behavior, and time constant of the phase transitions.
We introduce the use of pure molten ortho-phosphoric acid (o-H3PO4) as an electrolyte for selforganizing electrochemistry. This electrolyte allows for the formation of self-organized oxide architectures (one-dimensional nanotubes, nanochannels, nanopores) on metals such as tungsten that up to now were regarded as very difficult to grow self-ordered anodic oxide structures. In this work, we show particularly the fabrication of thick, vertically aligned tungsten oxide nanochannel layers, with pore diameter of ca. 10 nm, and illustrate their potential use in some typical applications.
Electrolyte gating using ionic liquid electrolytes has recently generated considerable interest as a method to achieve large carrier density modulations in a variety of materials. In noble metal thin films, electrolyte gating results in large changes in sheet resistance. The widely accepted mechanism for these changes is the formation of an electric double layer with a charged layer of ions in the liquid and accumulation or depletion of carriers in the thin film. We report here a different mechanism. In particular, we show using x-ray absorption near edge structure (XANES) that the previously …
Using a solid electrolyte to tune the carrier density in thin-film materials is an emerging technique that has potential applications in both basic and applied research. Until now, only materials containing small ions, such as protons and lithium ions, have been used to demonstrate the gating effect. Here, we report the study of a lab-synthesised sodium-ion-based solid electrolyte, which shows a much stronger capability to tune the carrier density in graphene than previously reported lithium-ion-based solid electrolyte. Our findings may stimulate the search for solid electrolytes better suited…
Ionic gating is a powerful technique to realize field-effect transistors (FETs) enabling experiments not possible otherwise. So far, ionic gating has relied on the use of top-electrolyte gates, which pose experimental constraints and make device fabrication complex. Promising results obtained recently in FETs based on solid-state electrolytes remain plagued by spurious phenomena of unknown origin, preventing proper transistor operation, and causing limited control and reproducibility. Here we explore a class of solid-state electrolytes for gating (Lithium-ion conducting glass-ceramics, LICGCs)…
Multilayered graphene-based nanoporous membranes with electrolyte incorporated between individual sheets is a unique nano-heterostructure system in which nanoconfined electrons in graphene and ions confined in between sheets are intimately coupled throughout the entire membrane. In contrast to the general notion that the electrolyte gating is unlikely to appear in multilayered graphene stacks, it is demonstrated in this work that the electrolyte gating effect in monolayer graphene can be transferred to its corresponding multilayered porous membranes. This gating effect presented on each indivi…
Tungsten oxide and its associated bronzes (compounds of tungsten oxide and an alkali metal) are well known for their interesting optical and electrical characteristics. We have modified the transport properties of thin WO$_3$ films by electrolyte gating using both ionic liquids and polymer electrolytes. We are able to tune the resistivity of the gated film by more than five orders of magnitude, and a clear insulator-to-metal transition is observed. To clarify the doping mechanism, we have performed a series of incisive operando experiments, ruling out both a purely electronic effect (charge ac…
We report electrical characterization of monolayer molybdenum disulfide (MoS2) devices using a thin layer of polymer electrolyte consisting of poly(ethylene oxide) (PEO) and lithium perchlorate (LiClO4) as both a contact-barrier reducer and channel mobility booster. We find that bare MoS2 devices (without polymer electrolyte) fabricated on Si/SiO2 have low channel mobility and large contact resistance, both of which severely limit the field-effect mobility of the devices. A thin layer of PEO/ LiClO4 deposited on top of the devices not only substantially reduces the contact resistance but also …
Ionic liquid gating has been used to modify properties of layered transition metal dichalcogenides (TMDCs), including two-dimensional (2D) crystals of TMDCs used extensively recently in the device work, which has led to observations of properties not seen in the bulk. The main effect comes from the electrostatic gating due to strong electric field at the interface. In addition, ionic liquid gating also leads to ion intercalation when the ion size of gate electrolyte is small compared to the interlayer spacing of TMDCs. However, the microscopic processes of ion intercalation have rarely been ex…
Pt ultrathin films on ferromagnetic insulators have been widely studied for spintronics applications, and magnetic moments of interface Pt atoms were considered to be ferromagnetically ordered due to a magnetic proximity effect (MPE). An anomalous Hall effect (AHE) is usually used to examine an out-of-plane magnetic moments of the Pt layer. To tune ferromagnetic properties of an Pt ultrathin film, we fabricated electric double layer transistors on Pt thin films with thicknesses of 5.9 nm and 7.0 nm on a $\rm{CoFe_2O_4}$ (CFO) ferrimagnetic insulator. For the Pt (7.0 nm)/CFO sample, a hysteresi…
Metallization of initially insulating VO2 via ionic liquid electrolytes (electrolyte gating) has recently been a topic of much interest. It is clear that the metallization takes place electrochemically and there has previously been extensive evidence for the removal of small amounts of oxygen during ionic liquid gating. Hydrogen intercalation has also been proposed, but the source of the hydrogen has remained unclear. In this work, solid-state magic angle spinning NMR spectroscopy is used to investigate the thermal metal-insulator transition in VO2, before progressing to catalytically hydrogen…
NiS$_2$ has been widely regarded as a model system to study the bandwidth-controlled Mott transition, as enabled by isovalent Se chemical substitution on the S sites. Motivated by advances in electrolyte gating, we theoretically investigate the filling-controlled Mott transition induced by gating, which has the advantage of avoiding dopant disorder and stoichiometric changes. We use combined Density Functional Theory (DFT) and Dynamical Mean Field Theory (DMFT) to study such a filling-controlled transition and compare it with the case of bandwidth control. We draw a temperature-filling phase d…
Electrolyte gating is a powerful technique for accumulating large carrier densities in surface two-dimensional electron systems (2DES). Yet this approach suffers from significant sources of disorder: electrochemical reactions can damage or alter the surface of interest, and the ions of the electrolyte and various dissolved contaminants sit Angstroms from the 2DES. Accordingly, electrolyte gating is well-suited to studies of superconductivity and other phenomena robust to disorder, but of limited use when reactions or disorder must be avoided. Here we demonstrate that these limitations can be o…
Electrical control of magnetism is a long-standing goal in physics and technology, recently developed electrolyte gating techniques providing a promising route to realization. Validating a recent theoretical prediction, here we demonstrate large enhancement of electrostatic modulation of ferromagnetic order in ion-gel-gated ultrathin La$_{0.5}$Sr$_{0.5}$CoO$_{3-δ}$ by thickness-tuning to the brink of a magnetic percolation transition. Application of only 3-4 V then drives a transition from a short-range-ordered insulator to a robust long-range ferromagnetic metal, realizing giant electrostatic…
Motivated by the existence of superconductivity in pyrite-structure CuS$_2$, we explore the possibility of ionic-liquid-gating-induced superconductivity in the proximal antiferromagnetic Mott insulator NiS$_2$. A clear gating-induced transition from a two-dimensional insulating state to a three-dimensional metallic state is observed at positive gate bias on single crystal surfaces. No evidence for superconductivity is observed down to the lowest measured temperature of 0.45 K, however. Based on transport, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, atomic force micr…
Electrochromic materials change color reversibly by applying an external DC voltage. One among the many emerging application of electro-chromics is the smart windows. The coloration efficiency, the optical colour modulation and the cyclability are the factors that bench mark the device. Tungsten oxide (WO3-x) is versatile material and reactive DC magnetron sputtering (with argon as sputter gas) technique is common for electro-chromics. In the present communication we have prepared tungsten oxide thin films by reactive DC magnetron sputtering technique (at room temperature 300 K) using Neon as …
We perform electric double-layer gating experiments on thin films of niobium nitride. Thanks to a cross-linked polymer electrolyte system of improved efficiency, we induce surface charge densities as high as $\approx 2.8 \times 10^{15}\,\mathrm{cm}^{-2}$ in the active channel of the devices. We report a reversible modulation of the superconducting transition temperature (either positive or negative depending on the sign of the gate voltage) whose magnitude and sign are incompatible with the confinement of the perturbed superconducting state to a thin surface layer, as would be expected within …
The temperature dependence of electric transport properties of single-layer and few-layer graphene at large charge doping is of great interest both for the study of the scattering processes dominating the conductivity at different temperatures and in view of the theoretically predicted possibility to reach the superconducting state in such extreme conditions. Here we present the results obtained in 3-, 4- and 5-layer graphene devices down to 3.5 K, where a large surface charge density up to about 6.8x10^14 cm^(-2) has been reached by employing a novel polymer electrolyte solution for the elect…
Ionic gating is a powerful technique for tuning the physical properties of a material via electric field-induced charge doping, but is prone to introduce extrinsic disorder and undesired electrochemical modifications in the gated material beyond pure electrostatics. Conversely, reversible, volatile and electrostatic modulation is pivotal in the reliable design and operation of novel device concepts enabled by the ultrahigh induced charge densities attainable via ionic gating. Here we demonstrate a simple and effective method to achieve reversible and volatile gating of surface-sensitive ultrat…
Transition metal dichalcogenides (TMDCs), together with other two-dimensional (2D) materials have attracted great interest due to the unique optical and electrical properties of atomically thin layers. In order to fulfill their potential, developing large-area growth and understanding the properties of TMDCs have become crucial. Here, we used molecular beam epitaxy (MBE) to grow atomically thin MoSe$_2$ on GaAs(111)B. No intermediate compounds were detected at the interface of as-grown films. Careful optimization of the growth temperature can result in the growth of highly aligned films with o…
We fabricate ion-gated field-effect transistors (iFET) on mechanically exfoliated multilayer MoS$_2$. We encapsulate the flake by Al$_2$O$_3$, leaving the device channel exposed at the edges only. A stable Li$^+$ intercalation in the MoS$_2$ lattice is induced by gating the samples with a Li-based polymeric electrolyte above $\sim$ 330 K and the doping state is fixed by quenching the device to $\sim$ 300 K. This intercalation process induces the emergence of anomalies in the temperature dependence of the sheet resistance and its first derivative, which are typically associated with structural/…
Magneto-ionics has emerged as a promising approach to manipulate magnetic properties, not only by drastically reducing power consumption associated with electric current based devices but also by enabling novel functionalities. To date, magneto-ionics have been mostly explored in oxygen-based systems, while there is a surge of interests in alternative ionic systems. Here we demonstrate highly effective hydroxide-based magneto-ionics in electrodeposited $α$-Co(OH)$_{2}$ films. The $α$-Co(OH)$_{2}$, which is a room temperature paramagnet, is switched to ferromagnetic after electrolyte gating wit…
Electrostatic doping in materials can lead to various exciting electronic properties, such as metal-insulator transition and superconductivity, by altering the Fermi level position or introducing exotic phases. Cd3As2, a three-dimensional (3D) analog of graphene with extraordinary carrier mobility, was predicted to be a 3D Dirac semimetal, a feature confirmed by recent experiments. However, most research so far has been focused on metallic bulk materials that are known to possess ultra-high mobility and giant magnetoresistance but limited carrier transport tunability. Here, we report on the fi…
