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Ionic-Liquid Gating in Two-Dimensional TMDs: The Operation Principles and Spectroscopic Capabilities.

ABSTRACT: Ionic-liquid gating (ILG) is able to enhance carrier densities well above the achievable values in traditional field-effect transistors (FETs), revealing it to be a promising technique for exploring the electronic phases of materials in extreme doping regimes. Due to their chemical stability, transition metal dichalcogenides (TMDs) are ideal candidates to produce ionic-liquid-gated FETs. Furthermore, as recently discovered, ILG can be used to obtain the band gap of two-dimensional semiconductors directly from the simple transfer characteristics. In this work, we present an overview of the operation principles of ionic liquid gating in TMD-based transistors, establishing the importance of the reference voltage to obtain hysteresis-free transfer characteristics, and hence, precisely determine the band gap. We produced ILG-based bilayer WSe₂ FETs and demonstrated their ambipolar behavior. We estimated the band gap directly from the transfer characteristics, demonstrating the potential of ILG as a spectroscopy technique.

SUBMITTER: Vaquero D

PROVIDER: S-EPMC8704478 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Direct imaging of structural changes induced by ionic liquid gating leading to engineered three-dimensional meso-structures.

Project description:The controlled transformation of materials, both their structure and their physical properties, is key to many devices. Ionic liquid gating can induce the transformation of thin-film materials over long distances from the gated surface. Thus, the mechanism underlying this process is of considerable interest. Here we directly image, using in situ, real-time, high-resolution transmission electron microscopy, the reversible transformation between the oxygen vacancy ordered phase brownmillerite SrCoO2.5 and the oxygen ordered phase perovskite SrCoO3. We show that the phase transformation boundary moves at a velocity that is highly anisotropic, traveling at speeds ~30 times faster laterally than through the thickness of the film. Taking advantage of this anisotropy, we show that three-dimensional metallic structures such as cylinders and rings can be realized. Our results provide a roadmap to the construction of complex meso-structures from their exterior surfaces.

| S-EPMC6076294 | biostudies-literature

Oxygen Displacement in Cuprates under Ionic Liquid Field-Effect Gating.

Project description:We studied structural changes in a 5 unit cell thick La1.96Sr0.04CuO4 film, epitaxially grown on a LaSrAlO4 substrate with a single unit cell buffer layer, when ultra-high electric fields were induced in the film by applying a gate voltage between the film (ground) and an ionic liquid in contact with it. Measuring the diffraction intensity along the substrate-defined Bragg rods and analyzing the results using a phase retrieval method we obtained the three-dimensional electron density in the film, buffer layer, and topmost atomic layers of the substrate under different applied gate voltages. The main structural observations were: (i) there were no structural changes when the voltage was negative, holes were injected into the film making it more metallic and screening the electric field; (ii) when the voltage was positive, the film was depleted of holes becoming more insulating, the electric field extended throughout the film, the partial surface monolayer became disordered, and equatorial oxygen atoms were displaced towards the surface; (iii) the changes in surface disorder and the oxygen displacements were both reversed when a negative voltage was applied; and (iv) the c-axis lattice constant of the film did not change in spite of the displacement of equatorial oxygen atoms.

| S-EPMC5006154 | biostudies-literature

Spectroscopic studies of amino acid ionic liquid-supported Schiff bases.

Project description:Amino acid ionic liquid-supported Schiff bases, derivatives of salicylaldehyde and various amino acids (L-threonine, L-valine, L-leucine, L-isoleucine and L-histidine) have been investigated by means of various spectroscopic techniques (NMR, UV-Vis, IR, MS) and deuterium isotope effects on ¹³C-NMR chemical shifts. The results have shown that in all studied amino acid ionic liquid-supported Schiff bases (except the L-histidine derivative) a proton transfer equilibrium exists and the presence of the COO? group stabilizes the proton transferred NH-form.

| S-EPMC6269710 | biostudies-literature

Thermoelectric Power in Bilayer Graphene Device with Ionic Liquid Gating.

Project description:The quest for materials showing large thermoelectric power has long been one of the important subjects in material science and technology. Such materials have great potential for thermoelectric cooling and also high figure of merit ZT thermoelectric applications. We have fabricated bilayer graphene devices with ionic-liquid gating in order to tune its band gap via application of a perpendicular electric field on a bilayer graphene. By keeping the Fermi level at charge neutral point during the cool-down, we found that the charge puddles effect can be greatly reduced and thus largely improve the transport properties at low T in graphene-based devices using ionic liquid gating. At (Vig, Vbg) = (-1 V, +23 V), a band gap of about 36.6 ± 3 meV forms, and a nearly 40% enhancement of thermoelectric power at T = 120 K is clearly observed. Our works demonstrate the feasibility of band gap tuning in a bilayer graphene using ionic liquid gating. We also remark on the significant influence of the charge puddles effect in ionic-liquid-based devices.

| S-EPMC4745055 | biostudies-other

Fast, comprehensive two-dimensional liquid chromatography.

Project description:The absolute need to improve the separating power of liquid chromatography, especially for multi-constituent biological samples, is becoming increasingly evident. In response, over the past few years, there has been a great deal of interest in the development of two-dimensional liquid chromatography (2DLC). Just as 1DLC is preferred to 1DGC based on its compatibility with biological materials we believe that ultimately 2DLC will be preferred to the much more highly developed 2DGC for such samples. The huge advantage of 2D chromatographic techniques over 1D methods is inherent in the tremendous potential increase in peak capacity (resolving power). This is especially true of comprehensive 2D chromatography wherein it is possible, under ideal conditions, to obtain a total peak capacity equal to the product of the peak capacities of the first and second dimension separations. However, the very long timescale (typically several hours to tens of hours) of comprehensive 2DLC is clearly its chief drawback. Recent advances in the use of higher temperatures to speed up isocratic and gradient elution liquid chromatography have been used to decrease the time needed to do the second dimension LC separation of 2DLC to about 20s for a full gradient elution run. Thus, fast, high temperature LC is becoming a very promising technique. Peak capacities of over 2000 and rates of peak capacity production of nearly 1 peak/s have been achieved. In consequence, many real samples showing more than 200 peaks with signal to noise ratios of better than 10:1 have been run in total times of under 30 min. This report is not intended to be a comprehensive review of 2DLC, but is deliberately focused on the issues involved in doing fast 2DLC by means of elevating the column temperature; however, many issues of broader applicability will be discussed.

| S-EPMC3205947 | biostudies-literature

Oxygen Vacancy in WO<sub>3</sub> Film-based FET with Ionic Liquid Gating.

Project description:Ionic liquid gating is a versatile method for inducing a metal-insulator transition in field-effect transistor device structures. The mechanism of carrier doping in metal oxide films is under debate. Ionic liquid gating of a WO3 film-based field effect transistor is discussed in this report. Flat and relatively smooth WO3 films were deposited on SrTiO3 substrates by pulsed laser deposition. Swept and constant gate voltage characteristics are measured in both argon and oxygen atmospheres. The results show a clear dependence on the oxygen pressure of the experimental chamber. Metallic behavior in the films is attributed to oxygen vacancy formation in the WO3 layer induced by the high electric field at the oxide-ionic liquid interface. The density of states of a monoclinic supercell of oxygen deficient WO3 was studied by density functional theory (DFT). Calculated W and O partial densities of states verify metallic behavior even at dilute oxygen vacancy concentrations and show the role of W and O orbitals in the conductivity.

| S-EPMC5612984 | biostudies-literature

Pressure-Dependent Clustering in Ionic-Liquid-Poly (Vinylidene Fluoride) Mixtures: An Infrared Spectroscopic Study.

Project description:The nanostructures of ionic liquids (ILs) have been the focus of considerable research attention in recent years. Nevertheless, the nanoscale structures of ILs in the presence of polymers have not been described in detail at present. In this study, nanostructures of ILs disturbed by poly(vinylidene fluoride) (PVdF) were investigated via high-pressure infrared spectra. For 1-(2-hydroxyethyl)-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([HEMIm][TFSI])-PVdF mixtures, non-monotonic frequency shifts of the C4,5-H vibrations upon dilution were observed under ambient pressure. The experimental results suggest the presence of microheterogeneity in the [HEMIm][TFSI] systems. Upon compression, PVdF further influenced the local structure of C4,5-H via pressure-enhanced IL-PVdF interactions; however, the local structures of C2-H and hydrogen-bonded O-H were not affected by PVdF under high pressures. For choline [TFSI]-PVdF mixtures, PVdF may disturb the local structures of hydrogen-bonded O-H. In the absence of the C4,5-H⋯anion and C2-H⋯anion in choline [TFSI]-PVdF mixtures, the O-H group becomes a favorable moiety for pressure-enhanced IL-PVdF interactions. Our results indicate the potential of high-pressure application for designing pressure-dependent electronic switches based on the possible changes in the microheterogeneity and electrical conductivity in IL-PVdF systems under various pressures.

| S-EPMC8400791 | biostudies-literature

NMR Spectroscopic Studies of Cation Dynamics in Symmetrically-Substituted Imidazolium-Based Ionic Liquid Crystals.

Project description:Ionic liquid crystals (ILCs) present a new class of non-molecular soft materials with a unique combination of high ionic conductivity and anisotropy of physicochemical properties. Symmetrically-substituted long-chain imidazolium-based mesogenic ionic liquids exhibiting a smectic liquid crystalline phase were investigated by solid state NMR spectroscopy and computational methods. The aim of the study was to reveal the correlation between cation size and structure, local dynamics, and orientational order in the layered mesophase. The obtained experimental data are consistent with the model of a rod-shaped cation with the two chains aligned in opposite directions outward from the imidazolium core. The alignment of the core plane to the phase director and the restricted conformations of the chain segments were determined and compared to those in single-chain counterparts. The orientational order parameter S~0.5-0.6 of double-chain ionic liquid crystals is higher than that of corresponding single-chain analogues. This is compatible with the enhanced contribution of van der Waals forces to the stabilization of smectic layers. Increased orientational order for the material with Br- counterions, which exhibit a smaller ionic radius and higher ability to form hydrogen bonds as compared to that of BF4-, also indicated a non-negligible influence of electrostatic and hydrogen bonding interactions. The enhanced rod-shape character and higher orientational order of symmetrically-substituted ILCs can offer additional opportunities in the design of self-assembling non-molecular materials.

| S-EPMC7404116 | biostudies-literature

Continuous Counter-Current Ionic Liquid Metathesis in Mixer-Settlers: Efficiency Analysis and Comparison with Batch Operation.

Project description:Following the initial cation formation, the synthesis of ionic liquids (ILs) often involves an anion-exchange or metathesis reaction. For hydrophobic ILs, this is generally performed through several cross-current contacts of the IL with a fresh salt solution of the desired anion. However, if a large number of contacts is required to attain an adequate conversion, this procedure is not economical because of the large excess of the reagent that is consumed. In this study, the metathesis of an IL, Aliquat 336 or [A336][Cl], to ILs with other anions ([A336][X] with X = HSO4 -, Br-, NO3 -, I-, and SCN-) was studied in a continuous counter-current mixer-settler setup. McCabe-Thiele diagrams were constructed to estimate the required number of stages for quantitative conversion. Significantly higher IL conversions were achieved, combined with reduced reagent consumption and waste production. This improvement in efficiency was most pronounced for anions placed low in the Hofmeister series, for example, HSO4 -, Br-, and NO3 -, which are difficult to exchange. The performance of the counter-current experiments was compared with the conventional multistep cross-current batch process by calculating the reaction mass efficiency (RME) and the environmental factor (E-factor). The RMEs of the cross-current experiments were notably smaller, that is, 38-78% of the values observed for the counter-current experiments. The E-factors of the counter-current experiments were a factor of 2.0-6.8 smaller than those of the cross-current experiments. These sustainability metrics indicate a highly efficient reagent use and a considerable, simultaneous decrease in waste production for the counter-current IL metathesis reactions.

| S-EPMC8767539 | biostudies-literature

Topological engineering of two-dimensional ionic liquid islands for high structural stability and CO<sub>2</sub> adsorption selectivity.

Project description:Ionic liquids (ILs) as green solvents and catalysts are highly attractive in the field of chemistry and chemical engineering. Their interfacial assembly structure and function are still far less well understood. Herein, we use coupling first-principles and molecular dynamics simulations to resolve the structure, properties, and function of ILs deposited on the graphite surface. Four different subunits driven by hydrogen bonds are identified first, and can assemble into close-packed and sparsely arranged annular 2D IL islands (2DIIs). Meanwhile, we found that the formation energy and HOMO-LUMO gap decrease exponentially as the island size increases via simulating a series of 2DIIs with different topological features. However, once the size is beyond the critical value, both the structural stability and electrical structure converge. Furthermore, the island edges are found to be dominant adsorption sites for CO2 and better than other pure metal surfaces, showing an ultrahigh adsorption selectivity (up to 99.7%) for CO2 compared with CH4, CO, or N2. Such quantitative structure-function relations of 2DIIs are meaningful for engineering ILs to efficiently promote their applications, such as the capture and conversion of CO2.

| S-EPMC8654070 | biostudies-literature

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