Chemistry of ruthenium as an electrode for metal-insulator-metal capacitor application.

Notwithstanding its excellent properties such as high work function and low resistance, Ru has not been widely applied in the preparation of electrodes for various electronic devices. This is because of the occurrence of severe morphological degradation in the actual devices employing Ru. Herein, we investigated Ru chemistry for electrode application and the degradation mechanism of Ru during subsequent processes such as thin film deposition or thermal annealing. We revealed that subsurface oxygen induces Ru degradation owing to the alteration of Ru chemistry by the pretreatment under various gas ambient conditions and due to the growth behavior of TiO2 deposited via atomic layer deposition (ALD). The degradation of Ru is successfully ameliorated by conducting an appropriate pretreatment prior to ALD. The TiO2 thin film deposited on the pretreated Ru electrode exhibited a rutile-phased crystal structure and smooth surface morphology, thereby resulting in excellent electrical properties. This paper presents an important development in the application of Ru as the electrode that can facilitate the development of various next-generation electronic devices.

High-Throughput Growth of Wafer-Scale Monolayer Transition Metal Dichalcogenide via Vertical Ostwald Ripening.

For practical device applications, monolayer transition metal dichalcogenide (TMD) films must meet key industry needs for batch processing, including the high-throughput, large-scale production of high-quality, spatially uniform materials, and reliable integration into devices. Here, high-throughput growth, completed in 12 min, of 6-inch wafer-scale monolayer MoS2 and WS2 is reported, which is directly compatible with scalable batch processing and device integration. Specifically, a pulsed metal-organic chemical vapor deposition process is developed, where periodic interruption of the precursor supply drives vertical Ostwald ripening, which prevents secondary nucleation despite high precursor concentrations. The as-grown TMD films show excellent spatial homogeneity and well-stitched grain boundaries, enabling facile transfer to various target substrates without degradation. Using these films, batch fabrication of high-performance field-effect transistor (FET) arrays in wafer-scale is demonstrated, and the FETs show remarkable uniformity. The high-throughput production and wafer-scale automatable transfer will facilitate the integration of TMDs into Si-complementary metal-oxide-semiconductor platforms.

An Atomically Thin Optoelectronic Machine Vision Processor.

2D semiconductors, especially transition metal dichalcogenide (TMD) monolayers, are extensively studied for electronic and optoelectronic applications. Beyond intensive studies on single transistors and photodetectors, the recent advent of large-area synthesis of these atomically thin layers has paved the way for 2D integrated circuits, such as digital logic circuits and image sensors, achieving an integration level of ≈100 devices thus far. Here, a decisive advance in 2D integrated circuits is reported, where the device integration scale is increased by tenfold and the functional complexity of 2D electronics is propelled to an unprecedented level. Concretely, an analog optoelectronic processor inspired by biological vision is developed, where 32 × 32 = 1024 MoS2 photosensitive field-effect transistors manifesting persistent photoconductivity (PPC) effects are arranged in a crossbar array. This optoelectronic processor with PPC memory mimics two core functions of human vision: it captures and stores an optical image into electrical data, like the eye and optic nerve chain, and then recognizes this electrical form of the captured image, like the brain, by executing analog in-memory neural net computing. In the highlight demonstration, the MoS2 FET crossbar array optically images 1000 handwritten digits and electrically recognizes these imaged data with 94% accuracy.

Vertical MoS2 Double-Layer Memristor with Electrochemical Metallization as an Atomic-Scale Synapse with Switching Thresholds Approaching 100 mV.

Atomically thin two-dimensional (2D) materials-such as transition metal dichalcogenide (TMD) monolayers and hexagonal boron nitride (hBN)-and their van der Waals layered preparations have been actively researched to build electronic devices such as field-effect transistors, junction diodes, tunneling devices, and, more recently, memristors. Two-dimensional material memristors built in lateral form, with horizontal placement of electrodes and the 2D material layers, have provided an intriguing window into the motions of ions along the atomically thin layers. On the other hand, 2D material memristors built in vertical form with top and bottom electrodes sandwiching 2D material layers may provide opportunities to explore the extreme of the memristive performance with the atomic-scale interelectrode distance. In particular, they may help push the switching voltages to a lower limit, which is an important pursuit in memristor research in general, given their roles in neuromorphic computing. In fact, recently Akinwande et al. performed a pioneering work to demonstrate a vertical memristor that sandwiches a single MoS2 monolayer between two inert Au electrodes, but it could neither attain switching voltages below 1 V nor control the switching polarity, obtaining both unipolar and bipolar switching devices. Here, we report a vertical memristor that sandwiches two MoS2 monolayers between an active Cu top electrode and an inert Au bottom electrode. Cu ions diffuse through the MoS2 double layers to form atomic-scale filaments. The atomic-scale thickness, combined with the electrochemical metallization, lowers switching voltages down to 0.1-0.2 V, on par with the state of the art. Furthermore, our memristor achieves consistent bipolar and analogue switching, and thus exhibits the synapse-like learning behavior such as the spike-timing dependent plasticity (STDP), the very first STDP demonstration among all 2D-material-based vertical memristors. The demonstrated STDP with low switching voltages is promising not only for low-power neuromorphic computing, but also from the point of view that the voltage range approaches the biological action potentials, opening up a possibility for direct interfacing with mammalian neuronal networks.

Triboelectric Series of 2D Layered Materials.

Recently, as applications based on triboelectricity have expanded, understanding the triboelectric charging behavior of various materials has become essential. This study investigates the triboelectric charging behaviors of various 2D layered materials, including MoS2 , MoSe2 , WS2 , WSe2 , graphene, and graphene oxide in a triboelectric series using the concept of a triboelectric nanogenerator, and confirms the position of 2D materials in the triboelectric series. It is also demonstrated that the results are obviously related to the effective work functions. The charging polarity indicates the similar behavior regardless of the synthetic method and film thickness ranging from a few hundred nanometers (for chemically exfoliated and restacked films) to a few nanometers (for chemical vapor deposited films). Further, the triboelectric charging characteristics could be successfully modified via chemical doping. This study provides new insights to utilize 2D materials in triboelectric devices, allowing thin and flexible device fabrication.

Two-Dimensional Materials Inserted at the Metal/Semiconductor Interface: Attractive Candidates for Semiconductor Device Contacts.

Metal-semiconductor junctions are indispensable in semiconductor devices, but they have recently become a major limiting factor precluding device performance improvement. Here, we report the modification of a metal/n-type Si Schottky contact barrier by the introduction of two-dimensional (2D) materials of either graphene or hexagonal boron nitride (h-BN) at the interface. We realized the lowest specific contact resistivities (ρc) of 3.30 nΩ cm2 (lightly doped n-type Si, ∼ 1015/cm3) and 1.47 nΩ cm2 (heavily doped n-type Si, ∼ 1021/cm3) via 2D material insertion are approaching the theoretical limit of 1.3 nΩ cm2. We demonstrated the role of the 2D materials at the interface in achieving a low ρc value by the following mechanisms: (a) 2D materials effectively form dipoles at the metal-2D material (M/2D) interface, thereby reducing the metal work function and changing the pinning point, and (b) the fully metalized M/2D system shifts the pinning point toward the Si conduction band, thus decreasing the Schottky barrier. As a result, the fully metalized M/2D system using atomically thin and well-defined 2D materials shows a significantly reduced ρc. The proposed 2D material insertion technique can be used to obtain extremely low contact resistivities in metal/n-type Si systems and will help to achieve major performance improvements in semiconductor technologies.

Selective detection of NO2 using Cr-doped CuO nanorods.

CuO nanosheets, Cr-doped CuO nanosheets, and Cr-doped CuO nanorods were prepared by heating a slurry containing Cu-hydroxide/Cr-hydroxide. Their responses to 100 ppm NO(2), C(2)H(5)OH, NH(3), trimethylamine, C(3)H(8), and CO were measured. For 2.2 at% Cr-doped CuO nanorods, the response (R(a)/R(g), R(a): resistance in air, R(g): resistance in gas) to 100 ppm NO(2) was 134.2 at 250 °C, which was significantly higher than that of pure CuO nano-sheets (R(a)/R(g) = 7.5) and 0.76 at% Cr-doped CuO nanosheets (R(a)/R(g) = 19.9). In addition, the sensitivity for NO(2) was also markedly enhanced by Cr doping. Highly sensitive and selective detection of NO(2) in 2.2 at% Cr-doped CuO nanorods is explained in relation to Cr-doping induced changes in donor density, morphology, and catalytic effects.

Design of highly sensitive C2H5OH sensors using self-assembled ZnO nanostructures.

Various ZnO nanostructures such as porous nanorods and two hierarchical structures consisting of porous nanosheets or crystalline nanorods were prepared by the reaction of mixtures of oleic-acid-dissolved ethanol solutions and aqueous dissolved Zn-precursor solutions in the presence of NaOH. All three ZnO nanostructures showed sensitive and selective detection of C(2)H(5)OH. In particular, ultra-high responses (R(a)/R(g) = ∼1,200, R(a): resistance in air, R(g): resistance in gas) to 100 ppm C(2)H(5)OH was attained using porous nanorods and hierarchical structures assembled from porous nanosheets, which is one of the highest values reported in the literature. The gas response and linearity of gas sensors were discussed in relation to the size, surface area, and porosity of the nanostructures.

Ultra-fast responding and recovering C2H5OH sensors using SnO2 hollow spheres prepared and activated by Ni templates.

Ultra-fast responding and recovering C(2)H(5)OH sensors were prepared using nanoscale SnO(2) hollow spheres with NiO-functionalized inner walls. The exceptional ultra-fast recovery characteristics were attributed to the catalytic surface reaction assisted by NiO at the inner shell.