Trevor A. Petach

A high-mobility electronic system at an electrolyte-gated oxide surface

Electrolyte gating is a powerful technique for accumulating large carrier densities at a surface. Yet this approach suffers from significant sources of disorder: electrochemical reactions can damage or alter the sample, and the ions of the electrolyte and various dissolved contaminants sit Angstroms from the electron system. 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 overcome by protecting the sample with a chemically inert, atomically smooth sheet of hexagonal boron nitride. We illustrate our technique with electrolyte-gated strontium titanate, whose mobility when protected with boron nitride improves more than 10-fold while achieving carrier densities nearing 1014 cm−2. Our technique is portable to other materials, and should enable future studies where high carrier density modulation is required but electrochemical reactions and surface disorder must be minimized.

Mechanism for the large conductance modulation in electrolyte-gated thin gold films

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 reported large conductance modulation in gold films is due to reversible oxidation and reduction of the surface rather than the charging of an electric double layer. We show that the double layer capacitance accounts for less than 10% of the observed change in transport properties. These results represent a significant step towards understanding the mechanisms involved in electrolyte gating.

Fully CMOS-compatible titanium nitride nanoantennas

CMOS-compatible fabrication of plasmonic materials and devices will accelerate the development of integrated nanophotonics for information processing applications. Using low-temperature plasma-enhanced atomic layer deposition (PEALD), we develop a recipe for fully CMOS-compatible titanium nitride (TiN) that is plasmonic in the visible and near infrared. Films are grown on silicon, silicon dioxide, and epitaxially on magnesium oxide substrates. By optimizing the plasma exposure per growth cycle during PEALD, carbon and oxygen contamination are reduced, lowering undesirable loss. We use electron beam lithography to pattern TiN nanopillars with varying diameters on silicon in large-area arrays. In the first reported single-particle measurements on plasmonic TiN, we demonstrate size-tunable darkfield scattering spectroscopy in the visible and near infrared regimes. The optical properties of this CMOS-compatible material, combined with its high melting temperature and mechanical durability, comprise a step towards fully CMOS-integrated nanophotonic information processing.

Voltage-Controlled Interfacial Layering in an Ionic Liquid on SrTiO3

One prominent structural feature of ionic liquids near surfaces is formation of alternating layers of anions and cations. However, how this layering responds to an applied potential is poorly understood. We focus on the structure of 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl) trifluorophosphate (BMPY-FAP) near the surface of a strontium titanate (SrTiO3) electric double-layer transistor. Using X-ray reflectivity, we show that at positive bias the individual layers in the ionic liquid double layer thicken and the layering persists further away from the interface. We model the reflectivity using a modified distorted crystal model with alternating cation and anion layers, which allows us to extract the charge density and the potential near the surface. We find that the charge density is strongly oscillatory with and without applied potential and that with an applied gate bias of 4.5 V the first two layers become significantly more cation rich than at zero bias, accumulating about 2.5 × 10(13) cm(-2) excess charge density.

Distinguishing Oxygen Vacancy Electromigration and Conductive Filament Formation in TiO2 Resistance Switching Using Liquid Electrolyte Contacts

Resistance switching in TiO2 and many other transition metal oxide resistive random access memory materials is believed to involve the assembly and breaking of interacting oxygen vacancy filaments via the combined effects of field-driven ion migration and local electronic conduction leading to Joule heating. These complex processes are very difficult to study directly in part because the filaments form between metallic electrode layers that block their observation by most characterization techniques. By replacing the top electrode layer in a metal-insulator-metal memory structure with easily removable liquid electrolytes, either an ionic liquid (IL) with high resistance contact or a conductive aqueous electrolyte, we probe field-driven oxygen vacancy redistribution in TiO2 thin films under conditions that either suppress or promote Joule heating. Oxygen isotope exchange experiments indicate that exchange of oxygen ions between TiO2 and the IL is facile at room temperature. Oxygen loss significantly increases the conductivity of the TiO2 films; however, filament formation is not observed after IL gating alone. Replacing the IL with a more conductive aqueous electrolyte contact and biasing does produce electroformed conductive filaments, consistent with a requirement for Joule heating to enhance the vacancy concentration and mobility at specific locations in the film.

Temperature-dependent optical properties of titanium nitride

The refractory metal titanium nitride is promising for high-temperature nanophotonic and plasmonic applications, but its optical properties have not been studied at temperatures exceeding 400 °C. Here, we perform in-situ high-temperature ellipsometry to quantify the permittivity of TiN films from room temperature to 1258 °C. We find that the material becomes more absorptive at higher temperatures but maintains its metallic character throughout visible and near infrared frequencies. X-ray diffraction, atomic force microscopy, and mass spectrometry confirm that TiN retains its bulk crystal quality and that thermal cycling increases the surface roughness, reduces the lattice constant, and reduces the carbon and oxygen contaminant concentrations. The changes in the optical properties of the material are highly reproducible upon repeated heating and cooling, and the room-temperature properties are fully recoverable after cooling. Using the measured high-temperature permittivity, we compute the emissivity, surf...

Disorder from the Bulk Ionic Liquid in Electric Double Layer Transistors

Ionic liquid gating has a number of advantages over solid-state gating, especially for flexible or transparent devices and for applications requiring high carrier densities. However, the large number of charged ions near the channel inevitably results in Coulomb scattering, which limits the carrier mobility in otherwise clean systems. We develop a model for this Coulomb scattering. We validate our model experimentally using ionic liquid gating of graphene across varying thicknesses of hexagonal boron nitride, demonstrating that disorder in the bulk ionic liquid often dominates the scattering.

Crystal truncation rods from miscut surfaces

Crystal truncation rods are used to study surface and interface structure. Since real surfaces are always somewhat miscut from a low index plane, it is important to study the effect of miscut on crystal truncation rods. We develop a model that describes the truncation rod scattering from miscut surfaces that have steps and terraces. We show that non-uniform terrace widths and jagged step edges are both forms of roughness that decrease the intensity of the rods. Non-uniform terrace widths also result in a broad peak that overlaps the rods. We use our model to characterize the terrace width distribution and step edge jaggedness on three SrTiO

Using Liquid Electrolytes in Dielectric Reliability Studies

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Fully CMOS-compatible TiN nanoantennas

(001) samples, showing excellent agreement between the model and the data, confirmed by atomic force micrographs of the surface morphology. We expect our description of terrace roughness will apply to many surfaces, even those without obvious terracing.